vvEPA
United States Environmental Monitoring Systems
Environmental Protection Laboratory
Agency Las Vegas NV 89114
EPA-600/4-83-040
September 1983
Research and Development
Characterization of
Hazardous Waste
Sites—A Methods
Manual:
Volume II. Available
Sampling Methods
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EPA-600/4-83-040
September 1983
CHARACTERIZATION OF HAZARDOUS
WASTE SITES—A METHODS MANUAL
VOLUME II
AVAILABLE SAMPLING METHODS
by
Patrick J. Ford
Paul J. Turina
Douglas E. Seely
GCA CORPORATION
GCA/TECHNOLOGY DIVISION
Bedford, Massachusetts 01730
Prepared for
Lockheed Engineering and Management
Services Company, Inc.
Las Vegas, Nevada, 89114
Under
EPA Contract No. 68-03-3050
EPA Project Officer
Charles K. Fitzsimmons
Advanced Monitoring Systems Division
Environmental Monitoring System Laboratory
Las Vegas, Nevada 89114
c.
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n 5, Liteary/e8t-^gl«soN BLVD.
», »L 60604-3590
ENVIRONMENTAL MONITORING SYSTEMS LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
LAS VEGAS, NEVADA 89114
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NOTICE
The information in this document has been funded wholly or in part by
the United States Environmental Protection Agency under contract number
68-03-3050 to Lockheed Engineering and Management Services Company, Inc.
and subcontract to GCA Corporation/Technology Division. It has been
subject to the Agency's peer and administrative review, and it has been
approved for publication. Mention of trade names or commercial products
does not constitute endorsement or recommendation for use.
o ;-.ii
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ABSTRACT
Investigations at hazardous waste and environment-threatening spill sites
inevitably require that onsite measurements and sampling activities be
conducted in order to assess the type and extent of contamination present.
Due to the nature of sites and materials under investigation, however, not all
sampling and measurement procedures may be applicable. It is important,
therefore, that personnel involved in hazardous waste investigations be aware
of the sampling procedures and measurement techniques most suited to their
needs.
This document is dedicated to sampling procedures and information, its
purpose being to present a compilation of methods and materials suitable to
address most needs that arise during routine waste site and hazardous spill
investigations. It is part of a multivolume manual entitled, Characterization
of Hazardous Waste Sites - A Methods Manual, developed by the U.S.
Environmental Protection Agency to serve a wide variety of users as a source
of information, methods, materials and references on the subject.
in
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CONTENTS
Abstract
Figures
Tables ix
1. Introduction i-i
Purpose 1-1
General 1-1
Method Selection Criteria 1-2
Purpose and Objectives of Sampling 1-3
Types of Samples 1-4
Sampling Plan 1-7
Sampling Schemes 1-8
Multiple Samples 1-9
Document Control/Chain-of-Custody 1-10
Safety 1-10
2. Solids 2-1
General 2-1
Soils 2-2
Method II-l: Soil Sampling with a Spade and
Scoop 2-4
Method II-2: Subsurface Solid Sampling with Auger
and Thin-Wall Tube Sampler 2-5
Sludges and Sediments 2-8
Method II-3: Collection of Sludge or Sediment
Samples with Scoop 2-9
Method II-4: Sampling Sludge or Sediments with a
Hand Corer 2-10
Method II-5: Sampling Bottom Sludges or Sediments
with a Gravity Corer 2-12
Method II-6: Sampling Bottom Sludges or Sediments
with a Ponar Grab 2-15
Bulk Materials 2-18
Method II-7: Sampling of Bulk Material with a
Scoop or Trier 2-19
Method II-8: Sampling Bulk Materials with a Grain
Thief 2-22
3. Liquids 3-1
General 3-1
Surface Waters 3-1
Method III-l: Sampling Surface Waters Using a
Dipper or Other Transfer Device 3-4
Method III-2: Use of Pond Sampler for the
Collection of Surface Water Samples 3-6
IV
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CONTENTS (continued)
Method III-3: Peristaltic Pump for Sampling
Surface Water Bodies 3-9
Method III-4: Collection of Water Samples from
Depth with a Kemmerer Bottle 3-13
Containerized Liquids 3-16
Method III-5: Collection of Liquid Containerized
Wastes Using Glass Tubes 3~18
Method I1I-6: Sampling Containerized Wastes Using
the Composite Liquid Waste Sampler (COLIWASA). . 3-21
Groundwater 3-24
Method III-7: Purging with a Peristaltic Pump . . 3-30
Method III-8: Purging with a Gas Pressure
Displacement System 3-31
Method III-9: Sampling Monitor Wells with a
Bucket Type Bailer 3-33
Method 111-10: Sampling Monitor Wells with a
Peristaltic Pump 3-36
4. Gases, Vapors and Aerosols 4-1
General 4-1
Ambient 4~1
Method IV-1: Determining Oxygen Content in
Ambient and Workplace Environments with a
Portable Oxygen Monitor 4-4
Method IV-2: Determination of Combustible Gas
Levels Using a Portable Combustible Gas
Indicator 4-6
Method IV-3: Monitoring Organic Vapors Using a
Portable Flame lonization Detector 4-9
Method IV-4: Monitoring Toxic Gases and Vapors
Using a Photoionization Detector 4-12
Method IV-5: Stain Detector Tube Method for
Sampling Gaseous Compounds 4-14
Method IV-6: Sampling for Volatile Organics in
Ambient Air Using Solid Sorbents 4-16
Method IV-7: Collecting Semivolatile Organic
Compounds Using Polyurethane Foam 4-25
Method IV-8: Determination of Total Suspended
Particulate in Ambient Air Using High Volume
Sampling Technique 4-30
Soil Gases and Vapors 4-36
Method IV-9: Monitoring Gas and Vapors from
Test Hole •. 4-37
Method IV-10: Monitoring Gas and Vapors from
Wells 4-39
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CONTENTS (continued)
Headspace Gases 4-42
Method IV-11: Sampling of Headspace Gases in
Semisealed Vessels 4-43
Method IV-12: Sampling of Headspace Gases in
Sealed Vessels 4-44
5. Ionizing Radiation 5-1
General 5-1
Personnel Monitors 5-2
Survey Instruments 5-3
Method V-l: Radiation Survey Instruments 5-6
6. References ..... 6-1
7. Bibliography 7-1
Appendices
A. Sample Containerization and Preservation A-l
B. Equipment Availability and Fabrication B-l
C. Packing and Shipping Guidelines C-l
D. Document Control/Chain-of-Custody Procedures . . D-l
E. Applicable Tables E-l
VI
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FIGURES
Number Page
1 Types of material 1-5
2 Auger and thin wall tube sampler 2-6
3 Hand corer 2-11
4 Gravity corers 2-13
5 Ponar grab 2-16
6 Sampling trier 2-20
7 Grain thief 2-23
8 Pond sampler 3-7
9 Peristaltic pump for liquid sampling 3-10
10 Peristaltic pump for liquid sampling (modified) 3~11
11 Modified Kemmerer sampler 3-14
12 Composite liquid waste sampler (COLIWASA) 3-22
13 Sample drillers log 3-25
14 Gas pressure displacement system 3-32
15 Teflon bailer , 3-34
16 Schematic of calibration system 4-21
17 Schematic of Tenax sampling train using backup cartridge. . 4-23
18 Schematic of Polyurethane Foam (PUF) sampling train for
collection of chlorinated pesticides and PCBs 4-28
VI1
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FIGURES (continued)
Number Page
19 Exploded view of typical high-volume air sampler parts. . . 4-31
20 Assembled sampler and shelter 4-31
21 Bar hole-maker 4-38
22 Gas sampling well 4-40
23 Drilling mechanism 4-45
Vlll
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TABLES
Number Page
1 Volatile Organics Collected with a Tenax Sorbent Sampling
System Using Parameters Outlined in Method IV-6 4-18
2 Literature Summary - Volatile Organics Amenable to
Collection by Tenax Sorbent Cartridges ..... 4-19
3 Organics Measured in Ambient Air Using PUF Procedures . . . 4-26
IX
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SECTION 1
INTRODUCTION
PURPOSE
This document is part of a raultivolume manual, entitled Characterization
of Hazardous Waste Sites—A Methods Manual, developed by the U.S. Environmental
Protection Agency. It is intended to serve a wide variety of users as a
source of information, with references, on the methods and materials needed to
characterize hazardous waste sites.
This Volume II—Available Sampling Methods is meant to be used in
conjunction with Volumes I, III, IV and V and is purposely dedicated to
sampling procedures and sampling information only. The intent is to describe
a collection of methods and materials sufficient to address most sampling
situations that arise during routine waste site and hazardous spill
investigations. It is by no means a panacea and will be updated periodically
as new information and improved methods become available. It includes a
compilation of methods, the purpose being to supply detailed, practical
information directed at providing field investigators with a set of functional
operating procedures.
Volume I—Integrated Approach to Hazardous Waste Site Characterization
includes discussions on preliminary assessment, initial data evaluation,
administrative procedures, offsite reconnaissance, site inspection, chain of
custody, quality assurance, safety and training in addition to considerations
concerning sampling strategy and methods selection. Volume III—Available
Laboratory Analytical Methods outlines detailed methodology suitable for
hazardous waste analysis and is organized by media and compound. Volume IV—
Safety will address safety aspects of hazardous waste sampling and handling.
GENERAL
Investigations at hazardous waste and environment-threatening spill sites
place more restrictive demands on personnel, materials and methodologies than
those usually found in routine environmental surveys. As a result,
traditional procedures and protocols used for the acquisition of environmental
samples often fail to meet the rigors and demands required for many hazardous
waste sampling applications. Thus, the collection of hazardous waste samples
will frequently require specialized equipment and protocols either developed
specifically for such uses or modified from preexisting materials and/or
techniques. Some important considerations are:
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• Methods and materials must be suitable to a wide range of situations
and applications because of the unknown nature of many hazardous
waste investigations and environmental spill responses.
• Hazardous wastes, by definition, are associated with both acute and
chronic exposure to dangerous, toxic chemicals and this dictates
that expeditious sample collection methods be used to minimize
personnel exposure.
• Because of the nature of the materials being sampled, the option of
using disposable sampling equipment must be considered because
attempting cleanup efforts in the field can be impractical.
• Hazardous waste site investigations and response actions at
environment-threatening spills generally require some level of
hazard protection that may be cumbersome, limit the field of vision,
or fatigue the sampler. Sample collection procedures must therefore
be relatively simple to follow to expedite sample procurement and to
reduce the chance of fatigue. Collection and monitoring equipment
should be simple to operate, direct reading, and should not be
unwieldy.
These and other factors associated with the procurement of hazardous waste
samples need to be addressed in a compilation of practical, cost effective,
and reliable methods and procedures capable of yielding representative samples
for a diverse number of potential parameters and chemical matrices. These
methods must be consonant with a variety of analytical considerations running
the gamut from gross compatibility analyses (pH, flammability, water
reactivity, etc.) to highly sophisticated techniques capable of resolution in
the part per billion (ppb) range.
METHOD SELECTION CRITERIA
Even a limited literature survey will disclose the existence of a great
number of sampling methods, all of which have certain merits that warrant
consideration. Therefore, selection criteria were chosen on which to base
decisions for including the sampling methods found in this manual. The
following is a listing, not necessarily in order of relative importance, of
these criteria.
Practicality
The selected methods should stress the use of simple, pragmatic, proven
procedures capable of being used or easily adapted to a variety of situations.
Representativeness
The essence of any sampling campaign is to collect samples that are
representative of the material or medium under consideration. The selected
methods, although strongly taking into consideration economics, simplicity,
practicality, and portability, must also be capable of delivering a true
representation of the situation under investigation.
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Economics
The costs of equipment, manpower and operational maintenance need to be
considered in relation to overall benefit. Instrument durability, disposable
equipment, cost of decontamination, and degree of precision and accuracy
actually required are also factors to be considered.
Simplicity or Ease of Operation
Because of the nature of the material to be sampled, the hazards
encountered during sampling, and the cumbersome safety equipment sometimes
required, the sampling procedures selected must be relatively easy to follow
and equipment simple to operate. Equipment should be portable, lightweight,
rugged and, if possible, direct reading.
Compatability with Analytical Considerations
The uncertainty of sample integrity as it relates to the analytical
techniques to be used should be reduced whenever possible. Errors induced by
poorly selected sampling techniques, especially those used in uncontrolled
situations, can be the weakest link in the quality of the generated data.
Special consideration must therefore be given to the selection of sampling
methods in relation to any adverse effects that might surface during
analysis. Proper materials of construction, sample or species loss, and
chemical reactivity are some of the factors that must receive attention.
Versatility
The diversity and sheer numbers of potential parameters and scenarios
often preclude the use of novel approaches that are designed or better suited
for classifying a small number of compounds in a limited, defined environment.
The methods in question must be adaptable to a variety of sampling situations
and chemical matrices. This factor should not, however, jeopardize sample
integrity.
Safety
The risk to sampling personnel, intrinsic safety of instrumentation, and
safety equipment required for conducting the sampling all need to be evaluated
in relation to the selection of proper methods and procedures.
The above criteria were consulted during the selection of each of the
methods listed in the following sections. Obviously, tradeoffs were necessary,
and therefore, some methods may prove excellent for some situations and less
satisfactory for others. This factor must be considered by any field
investigator before using the procedures outlined here.
PURPOSE AND OBJECTIVES OF SAMPLING
The basic objective of any sampling program is to produce a set of
samples representative of the source under investigation and suitable for
subsequent analysis. More specifically, the objective of sampling hazardous
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wastes is to acquire information that will assist investigators in identifying
unknown compounds present and to assess the extent to which these compounds
have become integrated into the surrounding environment. Subsequently, this
acquired information may be used in future litigations as well as to assist
investigators in the development of remedial actions.
The term "sample" can most simply be defined as a representative part of
the object to be analyzed. This definition needs to be qualified further,
however, by the consideration of several criteria.
Of utmost importance is representativeness. To meet the requirement of
representativeness, the sample needs to be chosen so that it possesses the
same qualities or properties as the material under consideration. However,
the sample needs only resemble the material to the degree determined by the
desired qualities under investigation and the analytical techniques used.
Sample size is also an important criterion to be considered. Sample size
must be carefully chosen with respect to the physical properties of the entire
object and the requirements and/or limitations of the analytical procedure.
For example, although the entire contents of an intact 55-gallon drum can
certainly be considered a representative sample of the drum material, it is an
impractical sample because of its bulk. Alternatively, too small a sample
size can be just as limiting, since representativeness and analytical volume
requirements might be jeopardized.
A third criterion for consideration is maintenance of sample integrity.
The sample must retain the properties of the parent object (at the time of
sampling) through collection, transport, and delivery to the analyst.
Degradation or alteration of the sample through exposure to air, excess heat
or cold, microorganisms, or to contaminants from the container must be avoided.
Finally, the number and/or the frequency of subsamples (e.g., samples
making up a composite) required and the distribution of these subsamples need
to be considered. These criteria are often dictated by the nature of the
material being sampled; that is, whether the material is homogeneous or
heterogeneous. For example, if a material is known to be homogeneous, a
single sample may suffice to define its quality. However, if a sample is
heterogeneous, a number of samples collected at specified time intervals or
distances may be necessary to define the characteristics of the subject
materials. In addition, the nature of the chemical parameters to be
identified and the way the analytical results will be used are also important
when the number and/or frequency of the samples to be collected are determined.
TYPES OF SAMPLES
Before defining the general sample types, the nature of the object or
materials under investigation must be discussed. Materials can be divided
into three basic groups as outlined in Figure 1.^
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Material
i
I
Homogeneous
No change of quality
throughout the material
He terogeneous
I
I
Discrete
Change of quality
throughout the material
I
Continuous
Change of quality
throughout the material
Homogeneous
Discrete Changes
Continuous Changes
Well-mixed liquids
Well-mixed gases
Pure metals
Ore pellets
Tablets
Crystallized rocks
Suspensions
Fluids or gases with gradients
Mixture of reacting compounds
Granulated materials with granules
much smaller than sample size
Source: Reference 1.
Figure 1. Types of material,
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Of least concern to the sampler are homogeneous materials. These
materials are generally defined as having uniform composition throughout. In
this case, any sample increment can be considered representative of the
material. On the other hand, heterogeneous samples present problems to the
sampler because of changes in the quality of the material over distance.
When discussing types of samples, it is important to distinguish between
the type of media to be sampled and the sampling technique that yields a
specific type of sample. In relation to the media to be sampled, two basic
types of samples can be considered: the environmental sample and the
hazardous sample.
Environmental samples (ambient air, soils, rivers, streams, or biota) are
generally dilute (in terms of pollutant concentration) and usually do not
require the special handling procedures used for concentrated wastes-
However, in certain instances, environmental samples can contain elevated
concentrations of pollutants and in such cases would have to be handled as
hazardous samples.
Hazardous or concentrated samples are those collected from drums, tanks,
lagoons, pits, waste piles, fresh spills, etc., and require special handling
procedures because of their potential toxicity or hazard. These samples can
be further subdivided based on their degree of hazard; however, care should be
taken when handling and shipping any wastes believed to be concentrated,
regardless of the degree.
In general, two basic types of sampling techniques are recognized, both
of which can be used for either environmental or concentrated samples.
Grab Samples
A grab sample is defined as a discrete aliquot representative of a
specific location at a given point in time. The sample is collected all at
once and at one particular point in the sample medium. The representativeness
of such samples is defined by the nature of the materials being sampled. In
general, as sources vary over time and distance, the representativeness of
grab samples will decrease.
Composite Samples
Composites are nondiscrete samples composed of more than one specific
aliquot collected at various sampling locations and/or different points in
time. Analysis of this type of sample produces an average value and can in
certain instances be used as an alternative to analyzing a number of
individual grab samples and calculating an average value. It should be noted,
however, that compositing can mask problems by diluting isolated
concentrations of some hazardous compounds below detection limits.
For sampling situations involving hazardous wastes, grab sampling
techniques are generally preferred because grab sampling minimizes the amount
of time sampling personnel must be in contact with the wastes, reduces risks
associated with compositing unknowns, and eliminates chemical changes that
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might occur due to compositing. Compositing is still often used for
environmental samples and may be used for hazardous samples under certain
conditions. For example, compositing of hazardous waste is often performed
(after compatibility tests have been completed) to determine an average value
over a number of different locations (group of drums). This procedure
provides data that can be useful by providing an average concentration within
a number of units, can serve to keep analytical costs down and can provide
information useful to transporters and waste disposal operations.
SAMPLING PLAN
Before any sampling activities are begun, it is imperative that the
purpose and goals of a program and the equipment, methodologies, and logistics
to be used during the actual sampling be identified in the form of a work or
sampling plan. This plan is developed when it becomes evident that a field
investigation is necessary and should be initiated in conjunction with or
immediately following the preliminary assessment. This plan should be clear
and concise and should detail the following basic components:
• background information collected during the preliminary assessment;
• objectives and goals of the investigation;
• sampling methods to be used, including equipment needs, procedures,
sample containment, and preservation;
• justification for selected methods and procedures;
• sample locations, as well as» number and types of samples to be
collected at each;
• organization of the investigative team;
• safety plan (includes safety equipment and decontamination
procedures, etc.);
• transportation and shipping information;
• training information; and
• additional site-specific information or requirements.
Note that this list of sampling plan components is by no means all
inclusive and that additional elements may be added or altered depending on
the specific requirements of the field investigation. It should also be
recognized that although a detailed sampling plan is quite important, it may
be an impractical undertaking in some instances. Emergency responses to
accidental spills would be a prime example of such an instance where time
might prohibit the development of a site-specific sampling plan. In such a
case, the investigator would have to rely on general guidelines and personal
judgment, and the sampling or response plan might be simply a strategy based
on preliminary information and finalized on site. In any event, a plan of
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action needs to be developed, no matter how concise or informal, to aid
investigators in maintaining a logical and consistent order to the
implementation of their task. Planning and safety are discussed in detail in
Volumes I, IV and V.
SAMPLING SCHEMES
The manner in which samples are selected generally falls into one of (or
a combination of) the following categories.
Random Sampling
Random sampling uses the theory of random chance probabilities to choose
representative sample locations. Random sampling is generally employed when
little information exists concerning the material, location, etc. It is most
effective when the population of available sampling locations is large enough
to lend statistical validity to the random selection process. Since one of
the main difficulties with random sampling deals with achieving a truly random
sample, it is advisable to use a table of random numbers to eliminate or
reduce bias (Appendix E).
Systematic Sampling
Systematic sampling involves the collection of samples at predetermined,
regular intervals. It is the most often employed sampling scheme, however,
care must be exercised to avoid bias; if, for example, there are periodic
variations in the material to be sampled such that the systematic plan becomes
partially phased with these variations.
A systematic sampling plan is often the end result for approaches that
are initiated as random due to the tendency of investigators to subdivide a
large sample area into increments prior to randomizing.
Stratified Sampling
Data and background information made available from the preliminary site
survey, prior investigations conducted on site and/or experience with similar
situations can be useful in reducing the number of samples needed to attain a
specified precision. Stratified sampling essentially involves the division of
the sample population into groups based on knowledge of sample characteristics
at these divisions. The purpose of the approach is to increase the precision
of the estimates made by sampling. This objective should be met if the
divisions are "selected in such a manner that the units within each division
are more homogeneous than the total population." The procedure used
basically involves handling each division in a simple random approach.
Judgment Sampling
A certain amount of judgment often enters into any sampling approach
used; however, this practice should be avoided whenever possible, especially
if the data generated are likely to be used for enforcement purposes.
Judgment approaches tend to allow investigator bias to influence decisions,
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and, if care is not exercised, can lead to poor quality data and improper
conclusions. If judgment sampling does become necessary, it is advisable that
multiple samples be collected in order to add some measure of precision.
Hybrid Sampling Schemes
In reality, most sampling schemes consist of a combination or hybrid of
the types previously described. For example, when selecting an appropriate
plan for sampling drums at a hazardous waste site, the drums might be
initially staged based on preliminary information concerning contents, 'program
objectives, etc. (judgment, stratified sampling), and then sampled randomly
within the specified population groups (random sampling). Hybrid schemes are
usually the method of choice as they can allow for greater diversity without
compromising the objectives of the program.
MULTIPLE SAMPLES
Multiple samples need to be collected at any time legal action is
anticipated. It is recommended that multiple samples be collected whenever
possible. These additional samples are essential to any quality control
aspects of the project and may also assist in reducing costs associated with
resampling brought about by container breakage, errors in the analytical
procedure, and data confirmation. The following is a list of the types of
multiple samples required.
Sample Blanks
Sample blanks are samples of deionized/distilled water, rinsed collection
devices or containers, sampling media (e.g., sorbent), etc. that are handled
in the same manner as the sample and subsequently analyzed to identify
possible sources of contamination during collection, preservation, handling,
or transport.
Duplicates
Duplicates are essentially identical samples collected at the same time,
in the same way, and contained, preserved, and transported in the same
manner. These samples are often used to verify the reproducibility of the
data.
Split Samples
Split samples are duplicate samples given to the owner, operator, or
person in charge for separate analysis.
Spiked Samples
Spiked samples are duplicate samples that have a known amount of a
substance of interest added to them. These samples are used to corroborate
the accuracy of the analytical technique and could be used as an indicator of
sample quality change during shipment to the laboratory.
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DOCUMENT CONTROL/CHAIN-OF-CUSTODY
Strict adherence to document and data control procedures is essential
from the standpoint of good quality assurance/quality control and should be
instituted as routine in any hazardous waste investigation. It becomes
especially important when collected data is used to support enforcement
litigations. All collected information, data, samples, and documents, must
therefore be accounted for and retrievable at any time during an investigation.
The purpose of document control is to ensure that all project documents
be accounted for when the project is complete. Types of documents considered
essential include maps, drawings, photographs, project work plans, quality
assurance plans, serialized logbooks, data sheets, coding forms, confidential
information, reports, etc.
Chain-of-custody procedures are necessary to document the sample
identity, handling and shipping procedures, and in general to identify and
assure the traceability of generated samples. Custody procedures trace the
sample from collection, through any custody transfers, and finally to the
analytical facility at which point internal laboratory procedures take over.
Chain-of-custody is also necessary to document measures taken to prevent
and/or detect tampering with samples, sampling equipment or the media to be
sampled. A detailed description of Document Control/Chain-of-Custody
Procedures can be found in Appendix D and in Volume I, Chapter 2.
SAFETY
Detailed safety considerations are adequately covered in Volume
IV—Safety, and Volume I, Section 3, and should be carefully reviewed betore
engaging in any hazardous waste sampling endeavors. It is important, however,
that safety be generally discussed at this time to provide a necessary
reminder of the importance of taking proper, well-developed precautions when
dealing with hazardous materials.
General Considerations
Field operations at sites containing hazardous substances pose potential
threats which could adversely affect the life and health of individuals
working onsite. Personnel performing any one of a number of tasks could be
exposed to a variety of acute and/or chronic hazards unless proper precautions
are taken prior to site entry. A comprehensive health and safety program must
therefore be emplaced in any organization currently involved in, or soon to be
associated with, onsite investigations of hazardous wastes.
In general, this program should include:
• a health surveillance program;
• an organizational safety program listing guidelines and standard
operating procedures;
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• training programs and refresher courses; and
• assignment of an organizational safety officer and/or officers.
In addition, a site-specific safety plan should be prepared that lists
protective measures required to guard the field investigation team from
site-specific hazards. This document should be drafted by the project team
leader and safety officer using all available information concerning the
site. It should include a designation of an onsite project coordinator (team
leader) and a site safety officer and, in general, the proper chain-of-command
to be followed when dealing with site-related matters. The site safety plan
should also include a listing of all safety equipment needed and the level of
protection necessary at all site areas; a reference of emergency information
including phone numbers of hospitals, ambulance services, fire and police
departments, etc.; directions to emergency facilities; and a reiteration of
the organizations general safety policies.
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, SECTIOU 2
SOLIDS
GENERAL
The sampling of solid or semi-solid materials is complicated by the
structural properties of the material. For example, the presence of entrapped
gases and fluids is often an integral part of the substance and of consequence
in the analytical techniques for which the sample was collected. It is
necessary in most cases to collect a sample which does not alter this
balance. In addition, physical strength and density of the material demand
sampling devices of significant rigidity and strength. As a result a great
deal of disturbance will occur at the sample-sampler interface. These effects
can be reduced by careful sampling and by collecting aliquots with a high
volume to surface area ratio.
A solid does not necessarily have uniform characteristics with respect to
distance or depth. Those portions which form boundaries with the container,
define the edges of a pile, or contact the atmosphere do not necessarily
represent the material as a whole. Care must be exercised in order to prevent
aeration or significant changes in moisture content. Samples should be
tightly capped and protected from direct light. Since most solids are usually
sampled in large quantities then returned to the laboratory for aliquoting and
analysis, preservation can in most cases be limited to refrigeration.
Most commercially available solids sampling devices are steel, brass or
plastic. In general, use of stainless steel is the most practical and several
manufacturers will fabricate their equipment with all stainless steel parts on
a special order basis. Another alternative is to have sampler contact
surfaces Teflon coated. This can be accomplished by either sending the device
to a commercial coater or by in-house application of spray-on Teflon
coatings. Some devices, especially those for soil sampling, have
traditionally been chrome- or nickel-plated steel. These should be
particularly avoided or the plating should be removed since scratches and
flaking of the plating can drastically effect the results of trace element
analysis.
This section is further divided into three subsections addressing the
sampling of soils, sludge and sediments, and bulk materials.
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SOILS
Soil sampling is an important adjunct to groundwater monitoring.
Sampling of the soil horizons above the groundwater table can detect
contaminants before they have migrated into the water table, and can help
establish the amount of contamination sorbed on aquifer solids that have the
potential of contributing to the groundwater contamination.
Soil types can vary considerably on a hazardous waste site. These
variations, along with vegetation, can effect the rate of contaminant
migration through the soil. It is important, therefore, that a detailed
record be maintained during sampling operations, particularly of location,
depth, and such characteristics as grain size, color and odor. Subsurface
conditions are often stable on a daily basis and may demonstrate only slight
seasonal variation especially with respect to temperature, available oxygen
and light penetration. Changes in any of these conditions can radically alter
the rate of chemical reactions or the associated microbiological community,
thus further altering conditions. As a result samples should be kept at their
at-depth temperature or lower, protected from direct light, sealed tightly in
glass bottles and analyzed as soon as possible.
The physical properties of the soil, its grain size, cohesiveness,
associated moisture and such factors as depth to bedrock and water table will
limit the depth from which samples can be collected and the method required to
collect them. Often this information on soil properties can be acquired from
published soil surveys obtainable through the U.S. Geological Surveys and
other government and farm agencies. A comprehensive listing of these offices
and currently available soil surveys is included in the "NEIC Manual for
Groundwater/Subsurface Investigations at Hazardous Waste Sites.'"* Most of
the methods employed for soil sampling at hazardous waste sites are
adaptations of techniques long employed by foundation engineers and
geologists. This section presents those methods which can be employed with a
minimum of special training, equipment or cost. More detailed methods capable
of sampling to greater depths, in more difficult soil conditions, or that can
simultaneously place groundwater monitor wells usually require professional
assistance. These techniques are discussed more fully in the "Manual for
Ground-water Sampling Procedures."^
Collection of samples from near the soil surface can be accomplished with
tools such as spades, shovels, and scoops. With this type of readily
available equipment the soil cover can be removed to the required depth; then
a stainless steel scoop can be used to collect the sample. An undisturbed
sample can be collected from this excavation by employing a thin wall tube
sampler. This device is, as the name implies, a metal tube generally 2.5 to
7.5 cm in diameter and 30.5 to 61.0 cm long. The tube is forced into the
soil, then extracted. Friction will usually hold the sample material in the
tube during the extraction. The construction material is generally steel, and
some samplers can utilize plastic liners and interchangable cutting tips. The
liners are useful for trace element sampling but are generally not suitable
for organic analysis due to the possibility that materials in the liner will
leach out and become incorporated as part of the sample. The liner tubes can
further be capped off and used as sample containers for transport to the lab.
2-2
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Interchangeable cutting tips facilitate smoother penetration with reduced
sample disturbance. They are available in various styles and construction
suitable for moist, dry, sandy or heavy-duty applications. The design of
these cutting tips will further aid in maintaining the sample in the tube
during sample extraction.
Kits are available that include, in conjunction with the tube sampler and
cutting tips, an auger point and a series of extension rods. These kits allow
for hand augering a borehole. The auger can then be removed and a tube
sampler lowered and forced into the soil at the completion depth. Though kits
are available with sufficient tools to reach depths in excess of 7 meters,
soil structure, impenetrable rock, and water levels usually prevent reaching
such completion depths. Kits that include 1 meter of drill rod and the
ability to order additional extensions will in practice prove satisfactory.
The need for soil information at greater depths will normally require
professional assistance. Consideration should be given to supplementing this
information with groundwater monitoring since soil sampling can be conducted
in conjunction with well completion.
For those wishing a more in-depth discussion of soils and soil sampling,
refer to the Protocol for Soil Sampling: Techniques and Strategies, (in
draft) by Dr. Benjamin J. Mason, prepared under contract to the U.S.
Environmental Protection Agency, Environmental Montoring Systems
Laboratory—Las Vegas (Contract No. CR808529-01-2), March 30, 1982. This
report discusses in detail the factors that influence the selection of a
particular sampling scheme or the use of a particular sampling method with a
strong emphasis on statistical design and data anlysis.
2-3
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METHOD II-l: SOIL SAMPLING WITH A SPADE AND SCOOP
Discussion
The simplest, most direct method of collecting soil samples for
subsequent analysis is with the use of a spade and scoop. A normal lawn or
garden spade can be utilized to remove the top cover of soil to the required
depth and then a smaller stainless steel scoop can be used to collect the
sample.
Uses
This method can be used in most soil types but is limited somewhat to
sampling the near surface. Samples from depths greater than 50 cm become
extremely labor intensive in most soil types. Very accurate, representative
samples can be collected with this procedure depending on the care and
precision demonstrated by the technician. The use of a flat, pointed mason
trowel to cut a block of the desired soil will be of aid when undisturbed
profiles are required. A stainless steel scoop or lab spoon will suffice in
most other applications. Care should be exercised to avoid the use of devices
plated with chrome or other materials. Plating is particularly common with
garden implements such as potting trowels.
Procedures for Use
1. Carefully remove the top layer of soil to the desired sample depth
with a spade.
2. Using a stainless steel scoop or trowel collect the desired quantity
of soil.
3. Transfer sample into an appropriate sample bottle with a stainless
steel lab spoon or equivalent.
4. Check that a Teflon liner is present in the cap if required. Secure
the cap tightly. The chemical preservation of solids is generally
not recommended. Refrigeration is usually the best approach
supplemented by a minimal holding time.
5. Label the sample bottle with the appropriate sample tag. Be sure to
label the tag carefully and clearly, addressing all the categories
or parameters. Complete all chain~of-custody documents and record
in the field log book.
6. Place the properly labeled sample bottle in an appropriate carrying
container maintained at 4°C throughout the sampling and
transportation period.
2-4
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METHOD II-2: SUBSURFACE SOLID SAMPLING WITH AUGER AND THIN-WALL TUBE SAMPLER
Discussion
This system consists of an auger bit, a series of drill rods, a "T"
handle, and a thin-wall tube corer (see Figure 2). The auger bit is used to
bore a hole to the desired sampling depth and then withdrawn. The auger tip
is then replaced with the tube corer, lowered down the borehole, and forced
into the soil at the completion depth. The corer is then withdrawn and the
sample collected.
Uses
This system can be used in a wide variety of soil conditions. It can be
used to sample both from the surface, by simply driving the corer without
preliminary boring, or to depths in excess of 6 meters. The presence of rock
layers and the collapse of the borehole, however, usually prohibit sampling at
depths in excess of 2 meters. Interchangable cutting tips on the corer reduce
the disturbance to the soil during sampling and aid in maintaining the core in
the device during removal from the borehole.
Procedures for Use
1. Attach the auger bit to a drill rod extension and further attach the
"T" handle to the drill rod.
2. Clear the area to be sampled of any surface debris (twigs, rocks,
litter). It may be advisable to remove the first 8 to 15 cm of
surface soil for an area approximately 15 cm in radius around the
drilling location.
3. Begin drilling, periodically removing accumulated soils. This
prevents accidentally brushing loose material back down the bore-
hole when removing the auger or adding drill rods.
4. After reaching desired depth, slowly and carefully remove auger from
boring.
5. Remove auger tip from drill rods and replace with thin-wall tube
sampler. Install proper cutting tip.
6. Carefully lower corer down borehole. Gradually force corer into
soil. Care should be taken to avoid scraping the borehole sides.
Hammering of the drill rods to facilitate coring should be avoided
as the vibrations may cause the boring walls to collapse.
7. Remove corer and unscrew drill rods.
8. Remove cutting tip and remove core from device.
2-5
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Figure 2. Auger and thin-wall tube sampler.
2-6
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9. Discard top of core (approximately 2.5 cm), which represents any
material collected by the corer before penetration of the layer in
question. Place remaining core into sample container.
10. Check that a Teflon liner is present in the cap if required. Secure
the cap tightly. The chemical preservation of solids is generally
not recommended. Refrigeration is usually the best approach
supplemented by a minimal holding time.
11. Label the sample bottle with the appropriate sample tag. Be sure to
label the tag carefully and clearly, addressing all the categories
or parameters. Complete all chain-of-custody documents and record
in the field logbook.
12. Place the properly labeled sample bottle in an appropriate carrying
container maintained at 4°C throughout the sampling and
transportation period.
Sources
deVera, E.R., Simmons, B.P., Stephens, R.D., and Storm, D.L. "Samplers
and Sampling Procedures for Hazardous Waste Streams." EPA 600/2-80-018,
January 1980.
2-7
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SLUDGES AND SEDIMENTS
In general and for the purpose of this manual, sludges will be defined as
semi-dry materials ranging from dewatered solids to high viscosity liquids.
Sediments are the deposited material underlying a body of water. On occasion
they are exposed by evaporation, stream rerouting, or other means of water
loss. In these instances they can be readily collected by soil or sludge
collection methods.
Sludges can often be sampled by the use of a stainless steel scoop or
trier. Frequently sludges form as a result of settling of the higher density
components of a liquid. In this instance the sludge may still have a liquid
layer above it. When the liquid layer is sufficiently shallow, the sludge may
be scooped up by a device such as the pond sampler described in Section III,
Method III-2, or preferably by using a thin-tube sampler as described in this
section (see Method II-4). The latter is preferable as it results in less
sample disturbance and will also collect an aliquot of the overlying liquid,
thus preventing drying or excessive sample oxidation before analysis. Sludges
which develop in 55-gallon drums can usually be collected by employing the
glass tubes used for the liquid portion sample (Method III-5) as a thin-tube
sampler. The frictional forces which hold the sludge in the tube can be
supplemented by maintaining a seal above the tube. When the overlying layer
is deep, a small gravity corer such as those used in limnological studies will
be useful. Gravity corers, such as Phlegers, are easier to preclean and
decontaminate than piston type corers.
If the sludge layer is shallow, less than 30 centimeters, corer
penetration may damage the container liner or bottom. In this instance a
Ponar or Eckman grab may be applicable, as grab samplers are generally capable
of only a few centimeters of penetration. Of the two, Ponar grab samplers are
more applicable to a wider range of sediments and sludges. They penetrate
deeper and seal better than the spring-activated Eckman dredges, especially in
granular substrates.
Sediments can be collected in much the same manner as described above for
sludges; however, a number of additional factors must be considered. Streams,
lakes, and impoundments, for instance, will likely demonstrate significant
variations in sediment composition with respect to distance from inflows,
discharges, or other disturbances. It is important, therefore, to document
exact sampling location by means of triangulation with stable references on
the banks of the stream or lake. In addition, the presence of rocks, debris,
and organic material may complicate sampling and preclude the use of or
require modification to some devices. Sampling of sediments should therefore
be conducted to reflect these and other variants.
2-8
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METHOD II-3: COLLECTION OF SLUDGE OR SEDIMENT SAMPLES WITH SCOOP
Discussion
Sludge and sediment samples are collected using the simple laboratory
scoop or garden type trowel specified in Method II-l. This method is more
applicable to sludges but it can be used for sediments provided the water
depth is very shallow (a few centimeters). It should be noted, however, that
this method can be disruptive to the water/sediment interface and might cause
substantial alterations in sample integrity if extreme care is not exercised.
The stainless steel laboratory scoop is generally recommended due to its
noncorrosive nature. Single grab samples may be collected or, if the area in
question is large, it can be divided into grids and multiple samples can be
collected and composited.
Uses
This method provides for a simple, quick, and easy means of collecting a
disturbed sample of a sludge or sediment.
Procedures for Use
1. Collect the necessary equipment and clean according to the
requirements for the analytical parameters to be measured.
2. Sketch the sample area or note recognizable features for future
reference.
3. Insert scoop or trowel into material and remove sample. In the case
of sludges exposed to air, it may be desirable to remove the first
1-2 cm of material prior to collecting sample.
4. If compositing a series of grab samples, use a stainless steel
mixing bowl or Teflon tray for mixing.
5. Transfer sample into an appropriate sample bottle with a stainless
steel lab spoon or equivalent.
6. Check that a Teflon liner is present in cap if required. Secure the
cap tightly. The chemical preservation of solids is generally not
recommended. Refrigeration is usually the best approach
supplemented by a minimal holding time.
7. Label the sample bottle with the appropriate sample tag. Be sure to
label the tag carefully and clearly, addressing all the categories
or parameters. Complete all chain-of-custody documents and record
in the field logbook.
8. Place the properly labeled sample bottle in an appropriate carrying
container maintained at 4°C throughout the sampling and
transportation period.
2-9
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METHOD II-4: SAMPLING SLUDGE OR SEDIMENTS WITH A HAND CORER
Discussion
This device is essentially the same type of thin-wall corer described for
collecting soil samples (Method H-2). It is modified by the addition of a
handle to facilitate driving the cover (see Figure 3) and a check valve on top
to prevent washout during retrieval through an overlying water layer.
Uses
Hand corers are applicable to the same situations and materials as the
scoop described in Method II-3. It has the advantage of collecting an
undisturbed sample which can profile any stratification in the sample as a
result of changes in the deposition.
Some hand corers can be fitted with extension handles which will allow
the collection of samples underlying a shallow layer of liquid. Most corers
can also be adapted to hold liners generally available in brass or
polycarbonate plastic. Care should be taken to choose a material which will
not compromise the intended analytical procedures.
Procedures for Use
1. Inspect the corer for proper precleaning.
2. Force corer in with smooth continuous motion.
3. Twist corer then withdraw in a single smooth motion.
4. Remove nosepiece and withdraw sample into a stainless steel or
Teflon tray.
5. Transfer sample into an appropriate sample bottle with a stainless
steel lab spoon or equivalent.
6. Check that a Teflon liner is present in cap if required. Secure the
cap tightly. The chemical preservation of solids is generally not
recommended. Refrigeration is usually the best approach
supplemented by a minimal holding time.
7. Label the sample bottle with the appropriate sample tag. Be sure to
label the tag carefully and clearly, addressing all the categories
or parameters. Complete all chain-of-custody documents and record
in the field logbook.
8. Place the properly labeled sample bottle in an appropriate carrying
container maintained at 4°C throughout the sampling and
transportation period.
2-10
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CHECK VALVE
NOSEPIECE
Figure 3. Hand corer.
2-11
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METHOD II-5: SAMPLING BOTTOM SLUDGES OR SEDIMENTS WITH A GRAVITY CORER
Discussion
A gravity corer is a metal tube with a replaceable tapered nosepiece on
the bottom and a ball or other type of check valve on the top. The check
valve allows water to pass through the corer on descent but prevents washout
during recovery. The tapered nosepiece facilitates cutting and reduces core
disturbance during penetration.
Most corers are constructed of brass or steel and many can accept plastic
liners and additional weights (see Figure 4).
Uses
Corers are capable of collecting samples of most sludges and sediments.
They collect essentially undisturbed samples which represent the profile of
strata which may develop in sediments and sludges during variations in the
deposition process. Depending on the density of the substrate and the weight
of the corer, penetration to depths of 75 cm (30 inches) can be attained.
Care should be exercised when using gravity corers in vessels or lagoons
that have liners since penetration depths could exceed that of substrate and
result in damage to the liner material.
Procedures for Use
1. Attach a precleaned corer to the required length of sample line.
Solid braided 5 mm (3/16 inch) nylon line is sufficient; 20 mm (3/4
inch) nylon, however, is easier to grasp during hand hoisting.
2. Secure the free end of the line to a fixed support to prevent
accidental loss of the corer.
3. Allow corer to free fall through liquid to bottom.
4. Retrieve corer with a smooth, continuous lifting motion. Do not
bump corer as this may result in some sample loss.
5. Remove nosepiece from corer and slide sample out of corer into
stainless steel or Teflon pan.
6. Transfer sample into appropriate sample bottle with a stainless
steel lab spoon or equivalent.
7. Check that a Teflon liner is present in cap if required. Secure the
cap tightly. The chemical preservation of solids is generally not
recommended. Refrigeration is usually the best approach
supplemented by a minimal holding time.
2-12
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NOSEPIECE
fr*
Figure 4. Gravity corers.
STABALIZING
FINS
2-13
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8. Label the sample bottle with the appropriate sample tag. Be sure to
label the tag carefully and clearly, addressing all the categories
or parameters. Complete all chain-of-custody documents and record
in the field logbook.
9. Place the properly labeled sample bottle in an appropriate carrying
container maintained at 4°C throughout the sampling and
transportation period.
Sources
American Public Health Association. "Standard Methods for the
Examination of Water and Wastewater" 14th Edition, Washington, B.C. 1975.
2-14
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METHOD II-6: SAMPLING BOTTOM SLUDGES OR SEDIMENTS WITH A PONAR GRAB
Discussion
The Ponar grab is a clamshell type scoop activated by a counter lever
system. The shell is opened and latched in place and slowly lowered to the
bottom. When tension is released on the lowering cable the latch releases and
the lifting action of the cable on the lever system closes the clamshell (see
Figure 5).
Uses
Ponars are capable of sampling most types of sludges and sediments from
silts to granular materials. They are available in a "Petite" version with a
232 square centimeter sample area that is light enough to be operated without
a winch or crane. Penetration depths will usually not exceed several
centimeters. Grab samplers, unlike the corers described in Method II-5, are
not capable of collecting undisturbed samples. As a result, material in the
first centimeter of sludge cannot be separated from that at lower depths. The
sampling action of these devices causes agitation currents which may
temporarily resuspend some settled solids. This disturbance can be minimized
by slowly lowering the sampler the last half meter and allowing a very slow
contact with the bottom. It is advisable, however, to only collect sludge or
sediment samples after all overlying water samples have been obtained.
Procedures for Use
1. Attach a precleaned Ponar to the necessary length of sample line.
Solid braided 5 mm (3/16 inch) nylon line is usually of sufficient
strength; however, 20 mm (3/4 inch) or greater nylon line allows for
easier hand hoisting.
2. Measure and mark the distance to bottom on the sample line. A
secondary mark, 1 meter shallower, will indicate proximity so that
lowering rate can be reduced, thus preventing unnecessary bottom
disturbance.
3. Open sampler jaws until latched. From this point on, support
sampler by its lift line or the sampler will be tripped and the jaws
will close.
4. Tie free end of sample line to fixed support to prevent accidental
loss of sampler.
5. Begin lowering the sampler until the proximity mark is reached.
6. Slow rate of descent through last meter until contact is felt.
7. Allow sample line to slack several centimeters. In strong currents
more slack may be necessary to release mechanism.
2-15
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5. Ponar
grab.
2-16
-------
8. Slowly raise dredge clear of surface.
9. Place Ponar into a stainless steel or Teflon tray and open. Lift
Ponar clear of the tray and return to lab for decontamination.
10. Collect a suitable aliquot with a stainless steel lab spoon or
equivalent and place sample into appropriate sample bottle.
11. Check for a Teflon liner in cap if required and secure cap tightly.
The chemical preservation of solids is generally not recommended.
Refrigeration is usually the best approach supplemented by a minimal
holding time.
12. Label the sample bottle with the appropriate sample tag. Be sure to
label the tag carefully and clearly, addressing all the categories
or parameters. Complete all chain-of-custody documents and record
in the field logbook.
13. Place the properly labeled sample bottle in an appropriate carrying
container maintained at 4°C throughout the sampling and
transportation period.
Sources
American Public Health Association. "Standard Methods for the
Examination of Water and Wastewater" 14th Edition, American Public Health
Association, Washington, D.C. 1975.
Lind, Owen T. "Handbook of Common Methods in Limnology." C.V. Mosby
Company, St. Louis, 1974.
2-17
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BULK MATERIALS
Unlike soils which are heterogeneous associations of earthen and
manufactured substances, bulk materials are generally a homogeneous collection
of a single identifiable product. They are usually contained in bags, drums
or hoppers although on occasion large amounts of the material may be piled
directly on the ground, either deliberately or as the result of a spill.
Those surfaces exposed to the atmosphere may undergo some chemical
alteration or degradation and should be avoided during sample collection.
Since the process producing the bulk material may demonstrate some variation
with respect to time, it is advisable to collect a series of samples as one
composite to represent the material.
Bulk materials in an unconsolidated state may be readily collected by a
stainless steel scoop. When the amount of the material is large, a composite
can be collected by the use of a grain thief (see Figure 7). This device is
essentially a long hollow tube with evenly spaced openings along its length.
This tube is placed inside an outer sleeve with similar openings and forced
into the material. The inner sleeve is rotated until its openings align with
those on the outer sleeve, thus allowing the material to enter. The inner
sleeve is then further rotated sealing the openings, the device is withdrawn,
and the sample recovered.
Grain thiefs are available in many materials including brass and various
plastics. As with other sampling devices, care should be taken to choose a
construction material which will not compromise the desired analytical results.
A more detailed treatment of this subject (Bulk Materials) can be found
in The Sampling of Bulk Materials by R. Smith and G. V. James, The Royal
Society of Chemistry, London (1981). Although this book does not deal
specifically with hazardous waste sampling, the concepts discussed, especially
on the subject of the establishment of a sampling scheme, are readily
applicable.
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METHOD 11-7: SAMPLING OF BULK MATERIAL WITH A SCOOP OR TRIER
Discussion
A typical sampling trier (Figure 6) is a long tube with a slot that
extends almost its entire length. The tip and edges of the tube slot are
sharpened to allow the trier to cut a core of the material to be sampled when
rotated after insertion into the material. Sampling triers are usually made
of stainless steel with wooden handles. They are about 61 to 100 cm long and
1.27 to 2.54 cm in diameter. They can be purchased readily from laboratory
supply houses.
A laboratory scoop or garden variety trowel can also be used to sample
bulk material. The trowel looks like a small shovel. The blade is usually
about 7 by 13 cm with a sharp tip. A laboratory scoop is similar to the
trowel, but the blade is usually more curved and has a closed upper end to
permit the containment of material. Scoops come in different sizes and
shapes. Stainless steel or polypropylene scoops with 7 by 15 cm blades are
preferred. A trowel can be bought from hardware stores; the scoop can be
bought from laboratory supply houses.
Uses
The use of the trier is similar to that of the grain sampler discussed in
Method II-8. It is preferred over the grain sampler when the powdered or
granular material to be sampled is moist or sticky.
The trowel or lab scoop can be used in some cases for sampling dry,
granular or powdered material in bins or other shallow containers. The lab
scoop is a superior choice since it is usually made of materials less subject
to corrosion or chemical reactions.
Procedures for Use
1. Insert the trier into the waste material at a 0 to 45° angle from
horizontal. This orientation minimizes the spillage of sample from
the sampler. Extraction of samples might require tilting of the
containers.
2. Rotate the trier once or twice to cut a core of material.
3. Slowly withdraw the trier, making sure that the slot is facing
upward.
4. Transfer the sample into a suitable container with the aid of a
spatula and/or brush.
5. If composite sampling is desired, repeat the sampling at different
points two or more times and combine the samples in the same sample
container.
2-19
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61-100 cm,
(24-40")
\
1.27-2.54 cm (%-!")
Source: Reference 6.
Figure 6. Sampling trier.
2-20
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6. Check that a Teflon liner is present in the cap if required. Secure
the cap tightly. The chemical preservation of solids is generally
not recommended. Refrigeration is usually the best approach
supplemented by a minimal holding time.
7. Label the sample bottle with the appropriate sample tag. Be sure to
label the tag carefully and clearly, addressing all the categories
or parameters. Complete all chain-of-custody documents and record
in the field logbook.
8. Place the properly labeled sample bottle in an appropriate carrying
container maintained at 4°C throughout the sampling and
transportation period.
Sources
deVera, E.R., Simmons, B.P., Stephens, R.D., and Storm, D.L. "Samplers
and Sampling Procedures for Hazardous Waste Streams." EPA-600/2-80-018.
January 1980.
2-21
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METHOD II-8: SAMPLING BULK MATERIALS WITH A GRAIN THIEF
Discussion
The grain thief (Figure 7) consists of two slotted telescoping tubes,
usually made of brass or stainless steel. The outer tube has a conical,
pointed tip on one end that permits the sampler to penetrate the material
being sampled. The sampler is opened and closed by rotating the inner tube.
Grain thiefs are generally 61 to 100 cm long by 1.27 to 2.54 cm in diameter,
and they are commercially available at laboratory supply houses.
Uses
The grain thief is used for sampling powdered or granular wastes or
materials in bags, fiberdrums, sacks or similar containers. This sampler is
most useful when the solids are no greater than 0.6 cm in diameter.
Procedures for Use
1. While the sampler is in the closed position, insert it into the
granular or powdered material or waste being sampled from a point
near a top edge or corner, through the center, and to a point
diagonally opposite the point of entry.
2. Rotate the inner tube of the sampler into the open position.
3. Wiggle the sampler a few times to allow materials to enter the open
slots.
4. Place the sampler in the closed position and withdraw from the
material being sampled.
5. Place the sampler in a horizontal position with the slots facing
upward.
6. Rotate and slide away the outer tube from the inner tube.
7. Transfer the collected sample in the inner tube into a suitable
sample container.
8. If composite sampling is desired, collect two or more core samples
at different points, and combine the samples in the same container.
9. Check that a Teflon liner is present in the cap if required. Secure
the cap tightly. The chemical preservation of solids is generally
not recommended. Refrigeration is usually the best approach
supplemented by a minimal holding time.
2-22
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61-100 cm,
(24-40")
-HK-
1.27-2.54 cm (%-!")
Source: Reference 6.
Figure 7. Grain thief,
2-23
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10. Label the sample bottle with the appropriate sample tag. Be sure to
label the tag carefully and clearly, addressing all the categories
or parameters. Complete all chain-of-custody documents and record
in the field logbook.
11. Place the properly labeled sample bottle in an appropriate carrying
container maintained at 4°C throughout the sampling and
transportation period.
Sources
deVera, E.R., Simmons, B.P., Stephens, R.D., and Storm, D.L. "Samplers
and Sampling Procedures for Hazardous Waste Streams." EPA-600/2-80-018.
January 1980.
Horwitz, W., Sensel, A., Reynolds, H., and Parks, D.L., editors. Animal
Feed: Sampling Procedure. In: Official Methods of Analysis. The
Association of Official Analytical Chemists. 12th Edition. Washington,
D.C. 1979.
2-24
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SECTION 3
LIQUIDS
GENERAL
Liquids by their nature are a relatively easy substance to collect.
Obtaining representative samples, however, is more difficult. Density,
solubility, temperature, currents, and a wealth of other mechanisms cause
changes in the composition of a liquid with respect to both time and
distance. Accurate sampling must be responsive to these dynamics and reflect
their actions.
For the purpose of this manual liquids will include both aqueous and
nonaqueous solutions and will be subdivided as surface waters, containerized
liquids, and ground waters. Surface waters will be considered as any fluid
body, flowing or otherwise, whose surface is open to the atmosphere. This
will include rivers, streams, discharges, ponds, and impoundments, both
aqueous and nonaqueous. The containerized liquid section will address
sampling of both sealed and unsealed containers of sizes varying from drums to
large tanks. Some overlap may occur between these two sections; when in
doubt, both sections should be consulted. The groundwater section will be
concerned with obtaining samples from subsurface waters but will not include
methods for well construction.
SURFACE WATERS
Samples from shallow depths can be readily collected by merely submerging
the sample container. The method is advantageous when the sample might be
significantly altered during transfer from a collection vessel into another
container. This is the case with samples collected for oil and grease
analysis since considerable material may adhere to the sample transfer
container and as a result produce inaccurately low analytical results.
Similarly the transfer of a liquid into a small sample container for volatile
organic analysis, if not done carefully, could result in significant aeration
and resultant loss of volatile species. Though simple, representative, and
generally free from substantial material disturbances, it has significant
shortcomings when applied to a hazardous waste, since the external surface of
each container would then need to be decontaminated.
In general the use of a sampling device, either disposable or constructed
of a nonreactive material such as glass, stainless steel, or Teflon, is the
most prudent method. The device should have a capacity of at least 500 ml, if
possible, to minimize the number of times the liquid must be disturbed, thus
reducing agitation of any sediment layers.
3-1
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A 1-liter stainless steel beaker with pour spout and handle works well.
It is easily cleaned and considerably less expensive than Teflon. Though
still more expensive than other plastics it is more durable and generally more
inert under field conditions. Also useful are large stainless steel ice
scoops and ladles available from commercial kitchen and laboratory supply
houses.
It is often necessary to collect liquid samples at some distance from
shore or the edge of the containment. In this instance an adaptation which
extends the reach of the technician is advantageous. Such a device is the
pond sampler as devised by the California Department of Health.° It
incorporates a telescoping heavy-duty aluminum pole with an adjustable beaker
clamp attached to the end (see Method III-2). The beaker previously
described, a disposable glass or plastic container, or the actual sample
container itself, can be fitted into the clamp. In situations where cross
contamination is of concern, use of a disposable container or the actual
sample container is always advantageous. The cost of properly cleaning
usually outweighs the cost of disposal of otherwise reusable glassware or
bottles. This is especially true when the cleanup must be done in the field.
The potential contamination of samples for volatile organic analysis by the
mere presence of organic solvents necessary for proper field cleaning is
usually too great to risk.
Another method of extending the reach of sampling efforts is the use of a
small peristaltic pump (see Method III-3). In this method the sample is drawn
in through heavy-wall Teflon tubing and pumped directly into the sample
container. This system allows the operator to reach out into the liquid body,
sample from depth, or sweep the width of narrow streams.
If a medical grade silicone tubing is used in the peristaltic pump, the
system is suitable for sampling almost any parameter including most
organics. ' Some volatile stripping, however, may occur, and though the
system may have a high flow rate, some material may be lost on the tubing.
Therefore, pumping methods should be avoided for sampling volatile organics or
oil and grease. Battery-operated pumps of this type are available and can be
easily hand-carried or carried with a shoulder sling. It is necessary in most
situations to change both the Teflon suction line as well as the silicon pump
tubing between sample locations to avoid cross-contamination. This requires
maintaining a sufficiently large stock of material to avoid having to clean
the tubing in the field.
These tubings are quite expensive but their relatively inert nature makes
thorough decontamination in the lab both practical and simple thus allowing
reuse. It should be noted that the Teflon suction tubing is an effective
substitute for that supplied with the sophisticated automatic liquid waste
samplers such as the ISCO Model 2100 and Manning Models S-3000 and S-4040.
When medical grade silicon tubing is not available or the analytical
requirements are particularly strict, the system can be altered as described
in Method III-3, Figure 10. In this configuration the sample volume
accumulates in the vacuum flask and does not enter the pump. The integrity of
the collection system can now be maintained with only the most nonreactive
3-2
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material contacting the sample. Some loss in lift ability will result since
the pump is now moving air, a compressible gas rather than an essentially
noncompressible liquid.
It may on occasion be necessary to sample large bodies of water where a
near surface sample will not sufficiently characterize the body as a whole.
In this instance again the above-mentioned pump is quite serviceable. It is
capable of lifting water from depths in excess of 6 meters. It should be
noted that this lift ability decreases somewhat with higher density fluids and
with increased wear on the silicone pump tubing. Similarly increases in
altitude will decrease the pumps ability to lift from depth. When sampling a
liquid stream which exhibits a considerable flow rate, it may be necessary to
weight the bottom of the suction line. The stainless steel strainer suction
weight supplied with the ISCO and Manning samplers usually works well. A
heavier weight can be constructed by filling a short (7.5 cm to 10 cm) length
of Teflon tubing with lead and plugging both ends with tight-fitting Teflon
plugs. This weight can then be clamped with stainless steel band clamps to
the suction tubing.
Situations may still arise where a sample must be collected from depths
beyond the capabilities of a peristaltic pump. In this instance an at-depth
sampler may be required. At present no such instrument made from
noncontaminating materials is commercially available. If such a system is
necessary it can be fabricated or an existing system can be modified by
replacing the rubber or plastic parts with Teflon or stainless steel. Care
should be taken in choosing a design that is easy to clean and decontaminate.
A Kemmerer-type sampler appears most applicable in its ability to be properly
modified and easily cleaned.
3-3
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METHOD III-l: SAMPLING SURFACE WATERS USING A DIPPER OR OTHER TRANSFER DEVICE
Discussion
A dipper or other container constructed of inert material, such as
stainless steel or Teflon, can be used to transfer liquid wastes from their
source to a sample bottle. This prevents unnecessary contamination of the
outer surface of the sample bottle that would otherwise result from direct
immersion in the liquid. Use of this device also prevents the technician from
having to physically contact the waste stream. Depending upon the sampling
application, the transfer vessel can be either disposed of or reused. If
reused, the vessel should be thorougly rinsed and/or decontaminated prior to
sampling a different source.
Uses
A transfer device can be utilized in most sampling situations except
those where aeration must be eliminated, such as volatile organic analysis or
where significant material may be lost due to adhesion to the transfer
container.
Procedures for Use
1. Submerge a stainless steel dipper or other suitable device with
minimal surface disturbance.
2. Allow the device to fill slowly and continuously.
3. Retrieve the dipper/device from the surface water with minimal
disturbance.
4. Remove the cap from the sample bottle and slightly tilt the mouth of
the bottle below the dipper/device edge.
5. Empty the dipper/device slowly, allowing the sample stream to flow
gently down the side of the bottle with minimal entry turbulence.
6. Continue delivery of the sample until the bottle is almost
completely filled. Leave adequate ullage to allow for expansion.
7. Preserve the sample if necessary as per guidelines in Appendix A.
8. Check that a Teflon liner is present in the cap if required. Secure
the cap tightly.
9. Label the sample bottle with an appropriate sample tag. Be sure to
label the tag carefully and clearly, addressing all the categories
or parameters. Record the information in the field logbook and
complete the chain-of-custody form.
3-4
-------
10. Place the properly labeled sample bottle in an appropriate carrying
container maintained at 4°C throughout the sampling and
transportation period.
11. Dismantle the sampler; wipe the parts with terry towels or rags and
store them in plastic bags for subsequent cleaning. Store used
towels or rags in garbage bags for subsequent disposal.
Sources
GCA Corporation, "Quality Assurance Plan, Love Canal Study - Appendix A,
Sampling Procedures," EPA Contract 68-02-3168.
3-5
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METHOD III-2: USE OF POND SAMPLER FOR THE COLLECTION OF SURFACE WATER SAMPLES
Discussion
The pond sampler consists of an adjustable clamp attached to the end of a
two- or three-piece telescoping aluminum tube that serves as the handle. The
clamp is used to secure a sampling beaker (see Figure 8). The sampler is not
commercially available, but it is easily and inexpensively fabricated. The
tubes can be readily purchased from most hardware or swimming pool supply
stores. The adjustable clamp and sampling beaker can be obtained from most
laboratory supply houses. The materials required to fabricate the sampler are
given in Appendix B.
Uses
The pond sampler is used to collect liquid waste samples from disposal
ponds, pits, lagoons, and similar reservoirs. Grab samples can be obtained at
distances as far as 3.5 m from the edge of the ponds. The tubular aluminum
handle may bow when sampling very viscous liquids if sampling is not done
slowly.
Procedures for Use
1. Assemble the pond sampler. Make sure that the sampling beaker and
the bolts and nuts that secure the clamp to the pole are tightened
properly.
2. With proper protective garment and gear, take grab samples by slowly
submerging the beaker with minimal surface disturbance.
3. Retrieve the pond sampler from the surface water with minimal
disturbance.
4. Remove the cap from the sample bottle and slightly tilt the mouth of
the bottle below the dipper/device edge.
5. Empty the sampler slowly, allowing the sample stream to flow gently
down the side of the bottle with minimal entry turbulence.
6. Continue delivery of the sample until the bottle is almost
completely filled.
7. Preserve the sample if necessary as per guidelines in Appendix A.
8. Check that a Teflon liner is present in the cap if required. Secure
the cap tightly.
9. Label the sample bottle with an appropriate sample tag. Be sure to
label the tag carefully and clearly, addressing all the categories
or parameters. Record the information in the field logbook and
complete the chain-of-custody documents.
3-6
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Varigrlp clamp
Bolt hole
Beaker, stainless
steel or disposable
Pole, telescoping, aluminum, heavy
duty, 250-450 cm (96-180")
Source: Reference 6.
Figure 8. Pond sampler.
3-7
-------
10. Place the properly labeled sample bottle in an appropriate carrying
container maintained at 4°C throughout the sampling and
transportation period.
11. Dismantle the sampler; wipe the parts with terry towels or rags and
store them in plastic bags for subsequent cleaning. Store used
towels or rags in garbage bags for subsequent disposal.
Sources
deVera, E.R., Simmons, B.P., Stephens, R.D., and Storm, D.L. "Samplers
and Sampling Procedures for Hazardous Waste Streams," EPA-600/2-80-018,
January 1980.
GCA Corporation, "Quality Assurance Plan, Love Canal Study - Appendix A,
Sampling Procedures," EPA Contract 68-02-3168.
3-8
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METHOD III-3: PERISTALTIC PUMP FOR SAMPLING SURFACE WATER BODIES
Discussion
This collection system consists of a peristaltic pump capable of
achieving a pump rate of 1 to 3 1pm, and an assortment of Teflon tubing for
extending the suction intake. A battery operated pump is preferable as it
eliminates the need for DC generators or AC inverters.
Uses
The system, as shown in Figures 9 and 10, is highly versatile. It is
portable and the sample collection is conducted through essentially chemically
nonreactive material. It is practical for a wide range of applications
including streams, ponds, and containers. This procedure can both extend the
lateral reach of the sampler and allow sampling from depth. Likewise, it can
function both as a well purge and a sample collection system. The chief
disadvantage of this method is the limited lift capacity of the pump,
approximately 8 meters.
Procedures for Use
1. Install clean, medical-grade silicone tubing in the pump head, as
per the manufacturer's instructions. Allow sufficient tubing on
discharge side to facilitate convenient dispensation of liquid into
sample bottles and only enough on the suction end for attachment to
the intake line. This practice will minimize sample contact with
the silicone pump tubing.
2. Select the length of suction intake tubing necessary to reach the
required sample depth and attach to intake side of pump tubing.
Heavy-wall Teflon, of a diameter equal to the required pump tubing,
suits most applications. (Heavier wall will allow for a slightly
greater lateral reach.)
3. If possible, allow several liters of sample to pass through system,
before actual sample collection. Collect this purge volume and then
return to source after the sample aliquot has been withdrawn.
4. Fill necessary sample bottles by allowing pump discharge to flow
gently down the side of bottle with minimal entry turbulence. Cap
each bottle as filled.
5. Preserve the sample if necessary as per guidelines in Appendix A.
6. Check that a Teflon liner is present in the cap if required. Secure
the cap tightly.
3-9
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MEDICAL GRADE SILICONE
TUBING
I
I-*
o
INTAKE
ASSORTED LENGTHS
OF TEFLON TUBING
PERISTALTIC
PUMP
DISCHARGE
TO SAMPLE CONTAINER
Source: Reference 7.
Figure 9. Peristaltic pump for liquid sampling.
-------
TEFLON CONNECTOR -7
6 MM 1.0. /
- TEFLON TUBING
6 MM O.D.
GLASS TUBING
6 MM 0.0.
LITER ERLENMEYER
OR SAMPLE BOTTLE
STOPPER TO FIT
FLASK OR SAMPLE BOTTLE
TYGON
TUBING
PERISTALTIC
PUMP
'OUTLET
Source: Reference 9.
Figure 10. Peristaltic pump for liquid sampling (modified)
3-11
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7. Label the sample bottle with an appropriate tag. Be sure to
complete the tag with all necessary information. Record the
information in the field logbook and complete the chain-of-custody
documents.
8. Place the properly labeled sample bottle in an appropriate carrying
container maintained at 4°C throughout the sampling and temperature
period.
9. Allow system to drain, then disassemble. Return tubing to lab for
decontamination (if feasible).
Sources
U.S. Environmental Protection Agency. "Procedures Manual for Ground
Water Monitoring at Solid Waste Disposal Facilities. EPA-530/SW-611.
August 1977.
3-12
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METHOD III-4: COLLECTION OF WATER SAMPLES FROM DEPTH WITH A KEMMERER BOTTLE
Discussion
The Ketnmerer bottle is a messenger-activated water sampling device (see
Figure 11). In the open position water flows easily through the device. Once
lowered to the desired depth a messenger is dropped down the sample line
tripping the release mechanism and closing the bottle. In the closed position
the bottle is sealed, both on top and bottom, from any additional contact with
the water column and can be retrieved.
Most commercially available Kemmerer bottles are of brass or plastic
construction. Modification of existing systems with nonreactive materials
such as Teflon, glass or stainless steel would be only partially successful
due to the complicated machining necessary for the release mechanism. Other
modifications such as a stoppered bottom drain are simpler and useful in
minimizing sample disturbance during transfer to the appropriate containers.
Uses
The Kemmerer bottle is currently the most practical method of collecting
discrete, at-depth samples from surface waters or vessels where the collection
depth exceeds the lift capacity of pumps. The application is limited however
by the incompatability of various construction materials with some analytical
techniques. Proper selection, i.e., all metal assemblies for organic analysis
or all plastic assemblies for trace element analysis, will overcome this
deficiency.
Procedures for Use
1. Inspect Kemmerer bottle for thorough cleaning and insure that sample
drain valve is closed (if bottle is so equipped).
2. Measure and then mark sample line at desired sampling depth.
3. Open bottle by lifting top stopper-trip head assembly.
4. Gradually lower bottle until desired level is reached (predesignated
mark from Step 2).
5. Place messenger on sample line and release.
6. Retrieve sampler; hold sampler by center stem to prevent accidental
opening of bottom stopper.
7. Rinse or wipe off exterior of sampler body (wear proper gloves and
protective clothing).
3-13
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BOTTOM
DRAIN
MESSENGER
CABLE
TRIP HEAD
UPPER STOPPER
CHAIN
CENTER ROD
BODY
LOWER STOPPER
Figure 11. Modified Kemmerer sampler.
3-14
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8. Recover sample by grasping lower stopper and sampler body with one
hand (gloved), and transfer sample by either (a) lifting top stopper
with other hand and carefully pouring contents into sample bottles,
or (b) holding drain valve (if present) over sample bottle and
opening valve.
9. Allow sample to flow slowly down side of sample bottle with minimal
disturbance.
10. Preserve the sample if necessary as per guidelines in Appendix A.
11. Check that a Teflon liner is present in the cap if required. Secure
the cap tightly.
12. Label the sample bottle with an appropriate tag. Be sure to
complete the tag with all necessary information. Record the
information in the field logbook and complete all chain-of-custody
records.
13. Place the properly labeled sample bottle in an appropriate carrying
container maintained at 4°C throughout the sampling and
transportation period.
14. Decontaminate sampler and messenger or place in plastic bag for
return to lab.
Sources
U.S. Environmental Protection Agency, "Procedures Manual for Ground Water
Monitoring at Solid Waste Disposal Facilities." EPA-530/SW-611, August
1977.
3-15
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CONTAINERIZED LIQUIDS
The sampling of tanks, containers, and drums present unique problems not
associated with natural water bodies. Containers of this sort are generally
closed except for small access ports, manways, or hatches on the larger
vessels or taps and bungs on smaller drums. The physical size, shape,
construction material, and location of access will limit the types of
equipment and methods of collection.
When liquids are contained in sealed vessels, gas vapor pressures build
up, sludges settle out, and density layerings develop. The potential for
explosive reactions or the release of noxious gases when containers are opened
requires considerable safeguards. The vessels should be opened with extreme
caution. Preliminary sampling of any headspace gases may be warranted.
Section IV details procedures for sampling headspace gases. As a minimum, a
preliminary check with an explosimeter or an organic vapor' analyzer will
determine levels of personnel protection and may be of aid in selecting a
sampling method.
In most cases it is impossible to observe the contents of these sealed or
partially sealed vessels. Since some layering or stratification is likely in
any solution left undisturbed over time, a sample must be taken that
represents the entire depth of the vessel.
Agitation to disrupt the layers and rehomogenize the sample is physically
difficult and almost always undesirable. In vessels greater than 1 meter in
depth the method of choice is to slowly, in known increments of length, lower
the suction line from a peristaltic pump. Discrete samples can be collected
from various depths then combined or analyzed separately. If the depth of the
vessel is greater than the lift capacity of the pump, an at-depth water
sampler, such as the Kemmerer type discussed in Method III-4, may be
required. In situations where the reactive nature of the contents are known,
a small submersible pump may be used.
When sampling a previously sealed vessel, a check should be made for the
presence of a bottom sludge. This is easily accomplished by measuring the
depth to apparent bottom then comparing it to the known interior depth.
Methods for sampling a bottom sludge are found in Section II.
The sampling of drums for hazardous liquid wastes is a very taxing
situation with present equipment. The most widely used method is a glass
tube, 6 mm to 16 mm I.D, that is lowered into the drum. The top of the tube
is sealed with a stopper or the thumb and the tube withdrawn. The bottom of
the tube is then placed over a glass jar, the stopper removed from the top and
the contents drained into the containers. After collection of sufficient
sample the tube is then broken up into the drum. This method is simple,
relatively inexpensive, and quick and collects a sample without having to
decontaminate equipment. It does, however, have serious drawbacks. Most low
density fluids do not hold well in the glass tubes. A great deal of the
potential sample flows out of the bottom of the tube as it is raised from the
drum, thereby reducing the representativeness of collected material. Many
3-16
-------
variations to this technique have been reported. These include the
incorporation of a small suction device (i.e., pipette bulb) to the top of the
tube as well as the use of various tube sizes. Some success has been reported
with tubes that have been heated at one end then drawn to form a much smaller
orifice. This allows the use of larger diameter tubing, therefore a greater
volume of sample per attempt, while reducing the material loss from the tube
bottom normally associated with larger diameter tubes.
It should be noted that in some instances disposal of the tube by
breaking it into the drum may interfere with eventual plans for the removal of
its contents. The use of this technique should therefore be cleared with the
project officer or other disposal techniques evaluated.
In many instances a drum containing waste material will have a sludge
layer on the bottom (Method III-5). Slow insertion of the sample tube down
into this layer and then a gradual withdrawal will allow the sludge to act as
a bottom plug to maintain the fluid in the tube. The plug can be gently
removed and placed into the sample container by the use of a stainless steel
lab spoon. These spoons are relatively inexpensive and can be disposed of in
the original waste container with the glass transfer tube.
Designs exist for equipment that will collect a sample from the full
depth of a drum and maintain it in the transfer tube until delivery to the
sample bottle. These designs include primarily the Composite Liquid Waste
Sampler (COLIWASA) and modifications thereof.6 The COLIWASA is difficult to
properly decontaminate in the field; its applicability is therefore limited to
those cases when a sample of the full depth of the drum is absolutely
necessary. The COLIWASA can be somewhat modified for this task by making the
lift rod of stainless steel, the bottom stopper of Teflon, and the body of
glass tubing. In this configuration the glass tube can be broken into the
drum leaving only the center rod and the stopper to be decontaminated. In a
preliminary investigation where the total number of drums to be sampled is
small an equal number of both the center rods and bottom stoppers could be
made in advance thus eliminating the time involved for onsite cleanup. Heat
shrinkable Teflon tubing or other types of Teflon coating can also be used to
cover the stainless steel rod if contact of the stainless steel with the waste
is undesirable.
3-17
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METHOD III-5: COLLECTION OF LIQUID CONTAINERIZED WASTES USING GLASS TUBES
Description
Liquid samples from opened containers (55-gallon drums) are collected
using lengths of glass tubing. The glass tubes are normally 122 cm in length
and 6 to 16 mm inside diameter. Larger diameter tubes may be used for more
viscous fluids if sampling with the small diameter tube is not adequate. The
tubing is broken up and discarded in the container after the sample has been
collected, eliminating difficult cleanup and disposal problems. This method
should not be attempted with less than a two-man sampling team.
Uses
This method provides for a quick, relatively inexpensive means of
collecting concentrated containerized wastes. The major disadvantage is from
potential sample loss which is especially prevalent when sampling less viscous
fluids. Splashing can also be a problem and proper protective clothing (e.g.,
butyl rubber apron, face shields, boot covers) should always be worn.
Procedures for Use
1. Remove cover from sample container opening.
2. Insert glass tubing almost to the bottom of the container. Try to
keep at least 30 cm of tubing above the top of the container.
3. Allow the waste in the drum to reach its natural level in the tube.
4. Cap the top of the tube with a safety-gloved thumb or a rubber
stopper.
5. Carefully remove the capped tube from the drum and insert the
uncapped end in the sample container.
6. Release the thumb or stopper on the tube and allow the sample
container to fill to approximately 90 percent of its capacity.
7. Repeat steps 2 through 6 if more volume is needed to fill the sample
container.
8. Remove the tube from the sample container and replace the tube in
the drum.
9. Cap the sample container tightly with a Teflon-lined cap and affix
the sample identification tag.
10. Break the glass sampling tube in such a way that all parts of it are
discarded inside the drum. (Note: see the initial discussion to
this section for exceptions.)
11. Replace the bung or place plastic over the drum.
3-18
-------
12. Place sample container in a Ziplock plastic bag (one per bag).
13. Place each bagged container in a 1-gallon metal paint can (or
appropriate sized container) and pack in vermiculite packing
material. Place lid on the can.
14. Mark the sample identification number on the outside of each paint
can and complete chain-of-custody log and the field logbook.
Optional Method (if sample of bottom sludge is desired)
1. Remove cover from container opening.
2. Insert glass tubing slowly almost to the bottom of the container.
Try to keep at least 30 cm of tubing above the top of the container.
3. Allow the waste in the drum to reach its natural level in the tube.
4. Gently push the tube towards the bottom of the drum into the sludge
layer. Do not force it.
5. Cap the top of the tube with a safely-gloved thumb or rubber stopper.
6. Carefully remove the capped tube from the drum and insert the
uncapped end in the sample container.
7. Release the thumb or stopper on the tube and allow the sample
container to fill to approximately 90 percent of its capacity. If
necessary, the sludge plug in the bottom of the tube can be
dislodged with the aid of a stainless steel laboratory spatula.
8. Repeat if more volume is needed to fill sample container and recap
the tube.
9. Proceed as in Steps 9 through 14 above.
Note:
1. If a reaction is observed when the glass tube is inserted (violent
agitation, smoke, light, etc.) the investigators should leave the
area immediately.
2. If the glass tube becomes cloudy or smokey after insertion into the
drum, the presence of hydrofluoric acid is indicated and a
comparable length of rigid plastic tubing should be used to collect
the sample.
3. When a solid is encountered in a drum (either layer or bottom
sludge) the optional method described above may be used to collect a
core of the material, or the material may be collected with a
disposable scoop attached to a length of wooden or plastic rod.
3-19
-------
Sources
American Society for Testing and Materials. "Standard Recommended
Practices for Sampling Industrial Chemicals," ASTM E-300-73.
U.S. Environmental Protection Agency, "Technical Methods for
Investigating Sites Containing Hazardous Substances, Technical Monograph
1-29, Draft," Ecology and the Environment, June 1981.
3-20
-------
METHOD III-6: SAMPLING CONTAINERIZED WASTES USING THE COMPOSITE LIQUID WASTE
SAMPLER (COLIWASA)
Discussion
The COLIWASA is a much cited sampler designed to permit representative
sampling of multiphase wastes from drums and other containerized wastes. The
sampler is commercially available or can be easily fabricated from a variety
of materials including PVC, glass, or Teflon. In its usual configuration it
consists ot a 152 cm by 4 cm (inside diameter) section of tubing with a
neoprene stopper at one end attached by a rod running the length of the tube
to a locking mechanism at the other end. Manipulation of the locking
mechanism opens and closes the sampler by raising and lowering the neoprene
stopper. A current recommended model of the COLIWASA is shown in Figure 12;
however, the design can be modified and/or adapted somewhat to meet the needs
of the sampler.
Uses
The COLIWASA is primarily used to sample most containerized liquids. The
plastic COLIWASA is reported to be able to sample most containerized liquid
wastes except for those containing ketones, nitrobenzene, dimethylforamide,
mesityloxide and tetrahydrofuran. A glass COLIWASA is able to handle all
wastes unable to be sampled with the plastic unit except strong alkali and
hydrofluoric acid solution. Due to the unknown nature of most containerized
waste, it would therefore be advisable to eliminate the use of PVC materials
and use samplers composed of glass or Teflon.
The major drawbacks associated with using a COLIWASA concern
decontamination and costs. The sampler is difficult if not impossible to
decontaminate in the field and its high cost in relation to alternative
procedures (glass tubes) make it an impractical throwaway item. It still has
applications, however, especially in instances where a true representation of
a multiphase waste is absolutely necessary. For this reason, the procedure
for its use is included.
Procedures for Use
1. Choose the material (see Appendix B) to be used to fabricate the
COLIWASA and assemble the sampler as shown in Figure 12.
2. Make sure that the sampler is clean.
3. Check to make sure the sampler is functioning properly. Adjust the
locking mechanism if necessary to make sure the neoprene rubber
stopper provides a tight closure.
4. Wear necessary protective clothing and gear and observe required
sampling precautions.
3-21
-------
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Figure 12. Composite liquid waste sampler (Coliwasa).
-------
5. Put the sampler in the open position by placing the stopper rod
handle in the T-position and pushing the rod down until the handle
sits against the sampler's locking block.
6. Slowly lower the sampler into the liquid waste. (Lower the sampler
at a rate that permits the levels of the liquid inside and outside
the sampler tube to be about the same. If the level of the liquid
in the sample tube is lower than that outside the sampler, the
sampling rate is too fast and will result in a nonrepresentative
sample).
7. When the sampler stopper hits the bottom of the waste container,
push the sampler tube downward against the stopper to close the
sampler. Lock the sampler in the closed position by turning the T
handle until it is upright and one end rests tightly on the locking
block.
8. Slowly withdraw the sampler from the waste container with one hand
while wiping the sampler tube with a disposable cloth or rag with
the other hand.
9. Carefully discharge the sample into a suitable sample container by
slowly pulling the lower end of the T handle away from the locking
block while the lower end of the sampler is positioned in a sample
container.
10. Cap the sample container with a Teflon-lined cap; attach label and
seal; record in field logbook; and complete sample analysis request
sheet and chain-of-custody record.
11. Unscrew the T handle of the sampler and disengage the locking
block. Clean sampler onsite or store the contaminated parts of the
sampler in a plastic storage tube for subsequent cleaning. Store
used rags in plastic bags for subsequent disposal.
Sources
deVera, E.R., Simmons, B.P., Stephens, R.D., and Storm, D.L. "Samplers
and Sampling Procedures for Hazardous Waste Streams." EPA 600/2-80-018,
January 1980.
3-23
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GROUNDWATER
Groundwater sampling suffers from many of the same difficulties as closed
containers, such as the inability to observe what is being collected or what
disturbances are resulting from that collection.
There are essentially two sources from which to collect groundwater,
either from wells or from seeps and springs. The former is more complex and a
discussion of its intricacies will follow later. The sampling of seeps and
springs is considerably easier, but it is less indicative of the actual
groundwater quality than well sampling.
Seeps and springs are generally areas where the surface contour
intersects the water table. These areas usually have well established
microbiological populations evidenced by extensive moss and algal growths.
These microbiological populations usually extend for some distance into the
water-bearing formation (aquifer) and are generally more populous and of
different species than those associated with the bulk of the aquifer. Their
effect on the oxygen content, pH, nutrient and metals concentrations in the
groundwater can be extensive. The water, therefore, that seeps from these
areas may be substantially altered, and not representative of the conditions
deeper in the subsurface. They can, however, yield some information if
properly interpreted. If the area in question is without developed wells they
are certainly worth consideration, especially for the ease with which they can
be sampled.
A stainless steel scoop of the type found in ice machines is ideal for
collecting samples from seeps. The flat bottom can be pressed against the
bank and the water will flow with very little additional disturbance into the
scoop, for transfer to the sample bottles. It is important to collect the
sample as close to the actual seep as possible to reduce contact time with the
atmosphere and potential for surface contamination.
For the purposes of this document, groundwater monitoring via wells will
include only the actual sampling of existing wells. The methods and
techniques for placement, construction, and development of wells for
groundwater monitoring are varied and complicated. The "Manual for
Ground-Water Sampling Procedures' and "NEIC Manual for Groundwater/
Subsurface Investigations at Hazardous Waste Sites1"* provide considerable
information for establishing a full groundwater monitoring program including
the completion of monitor wells. It is, however, necessary to know the well
depth, diameter, construction material, type and size of the well screen if
used, vertical position of the well screen or slotted section of casing, and
type of annular packing if any. This information will aid in evaluating the
suitability of the well for sampling for a particular analysis. For instance,
if the well has a galvanized steel casing with a brass well screen, it would
not be suitable for trace element analysis. Similarly, if the well is located
in a swampy area, the type and amount of grout or fill around the well casing
would determine the degree of surface water inflow to the well that might be
expected. Most of the information necessary is available on the well drillers
log. An example of a completed drillers log is included as Figure 13. It
should be noted, however, that the actual well depth may be somewhat less than
3-24
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GROUND
-i
LJ
IH
q
3
D
1
1
U
w
o a!
— i u
c/i
1
• 1
•-CASING — *
— — ~
— — —
— — —
— ~ Z
— — —
= ~ E
T
_LJLEVEL
WELL LOG
AIR
TRASH
SAND & STONES
FEET
FROM GROUND
SURFACE
0- 3
3-10
10-20
NAME OF OWNER
JOB = 1393
LOCATION
WELL NO. SAMPLING WELL 4
MRS. PUMPED N/A
CAPACITY G.P.M. N/A
STATIC LEVEL 11 '
PUMPING LEVEL N/A
SPECIFIC CAPACITY N/A
DIAMETER OF WELL 8-3/4
DEPTH OF WELL (ground) 17'
LENGTH OF CASING 10'
DISTANCE TO TOP OF PACKER (g)
TYPE SCREEN PVC
SIZE OF SCREEN 4"
LENGTH OF SCREEN 10'
TOP SCREEN FITTING COUPLING
BOTTOM SCREEN FITTING CAP
BLANK NONE
SLOT SIZE .020
DRILLING MACHINE NO. D-5
DRILLER
GRAVEL #2
BAGS OF CEMENT CLAY
DATE WELL COMPLETED 7/9/77
Rotary table approx. 3" above ground level
Figure 13. Sample drillers log.
3-25
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the completion depth listed on the log as a result of aquifer invasion through
the screen or open-hole sloughing below the casing. This may be particularly
noticable in wells that have had only sporadic use or have been idle long. It
is recommended then that actual well depth be checked by field measurement
whenever possible.
Measurement of the well depth can be accomplished by sounding the well
with a reusable weight attached to a disposable line. Slowly lower the weight
into the well until the bottom is detected. With the line taut, mark the top
of casing level on the line with waterproof ink. Recover the line and weight
from the well and accurately measure the length of line below the mark.
Discard the line and thoroughly clean the weight before reuse. Next, measure
the casing length above (or below) ground level and subtract (or add) to
obtain well depth. -> When measuring potentially contaminated wells, wear
appropriate safety gear to avoid skin contact with well water.
The depth to the water level in the well must be measured in order to
calculate the liquid bore volume for prepurging and is also important to any
hydrological interpretations of the analytical results. Depths to water are
normally measured with respect to the top of casing, as in well-depth
determinations. Several methods are available including: (1) the electric
sounder, (2) the chalked steel tape, and (3) the popper.-*
The electric sounder, although not the most accurate, is recommended for
initial site work because of the minimal potential for equipment contamination
and simplicity of use. Sounders usually consist of a conductivity cell at the
end of a graduated wire, and a battery powered buzzer. When the cell contacts
the water the increased conductivity completes the circuit and allows current
to flow to the alarm buzzer. The depth to water can then be read from the
graduations on the wire or the wire can be measured directly.
The chalked steel tape is a more accurate device for measuring static
water levels. Coat the lower 1 to 1.5 meters of a steel measuring tape on
either side with either carpenter's chalk or any of the various indicating
pastes. Attach a weight to the lower end to keep the tape taut and lower it
into the center of the well (condensate on the casing wall may prematurely wet
the tape). Listen for a hollow "plopping" sound when the weight reaches
water. Then lower the tape very slowly for at least another 15 cm, preferably
to an even increment. Next, carefully withdraw the tape from the well;
determine water depth by subtracting the wetted length of tape from the total
length of tape in the well. In small-diameter wells, the volume of the weight
may cause the water to rise by displacement. Thoroughly clean the wetted
section of the tape and the weight before reuse to avoid cross contamination.
The metal tape and popper is another simple and reliable method for
measuring depth to water in wells more than 3.8 cm (1.5 in.) in diameter. The
popper is a metal cylinder with a concave undersurface fastened to the end of
the metal tape. Raise and drop the popper until it hits the water surface and
makes a distinct "popping" sound. Adjust the tape length so that the popper
just hits the water surface. Read the depth to water from the tape measure.
3-26
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To obtain a representative sample of the groundwater it must be
understood that the composition of the water within the well casing and in
close proximity to the well is probably not representative of the overall
groundwater quality at that sampling site. This is due to the possible
presence of drilling contaminants near the well and because important
environmental conditions such as the oxidation-reduction potential may differ
drastically near the well from the conditions in the surrounding water-bearing
materials. For these reasons it is highly desirable that a well be pumped or
bailed until the well is thoroughly flushed of standing water and contains
fresh water from the aquifer. The recommended amount of purging before
sampling is dependent on many factors including the characteristics of the
well, the hydrogeological nature of the aquifer, the type of sampling
equipment being used, and the parameters being sampled. A common procedure is
to pump or bail the well until a minimum of two (2) to ten (10) bore-volumes
have been removed.
Gibb1 notes that removing all water from the well bore is only
possible if the well is pumped dry and suggests two alternative approaches:
(a) monitor the water level in the well while pumping. When the water level
has "stabilized" most if not all of the water being pumped is coming from the
aquifer. (b) monitor the temperature, conductivity, or pH of the water while
pumping. When these parameters "stabilize" it is probable that little or no
water from casing storage is being pumped."
The use of an indicating analysis such as pH, temperature, redox
potential, or, most commonly, conductivity, may be the most accurate and
reliable method of assuring complete well purging. The technique is easily
implemented in the field and gives a rapid and positive indication of changes
in the well bore water. This change in the water character and subsequent
stabilization can normally be interpreted as evidence that sufficient purging
has occurred. It should be noted that the sensitivity of these parameters to
changes as a result of exposure of groundwater to surface level conditions
(i.e., changes in the partial pressure of dissolved gases or the conditions of
the purging system) make in-situ monitoring desirable. An alternative to this
would be to conduct these measurements in a closed cell attached to the
discharge side of the pump system.
Other factors which will influence the amount of purging required before
sampling include the pumping rate and the placement of the pumping equipment
within the column of water in the well bore. For example, recent studies have
shown that if a pump is lowered immediately to the bottom of a well before
pumping, it may take some time for the column of water above it to be
exchanged if the transmissivity of the aquifer is high and the well screen is
at the bottom of the casing.9.10 jn suc^ cases the pump will be drawing
water primarily from the aquifer.
This has been further documented in studies conducted by the National
Council of the Paper Industry for Air and Stream Improvement (NCASI)° on a
full-scale model of a 2-inch PVC well. They found that purging from just
below the water surface insured a more complete removal of the casing water
than by withdrawal from well below the surface. It was also evident that when
3-27
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purging did occur from just below the surface, satisfactory results could be
obtained at any of a wide range of pumping rates with either a peristaltic or
a submersible pump.
Because of the potential for further environmental contamination,
planning for purge water disposal is a necessary part of well monitoring.
Alternatives range from dumping it on the ground (not back down the well) to
full containment, treatment, and disposal. If the well is believed to be
contaminated, the best practice is to contain the purge water and store it
until the water samples have been analyzed. Once the contaminants are
identified, appropriate treatment requirements can be determined.
There are many methods available for well purging. In some cases bailing
will suffice, however it can become tedious and labor intensive in deep or
large diameter wells. Submersible pumps are often the best choice but most
that are readily available to investigators are heavy, awkward and will not
fit smaller diameter wells. Models have been on the market for the past few
years that will fit inside a 2-inch diameter well; however, they can be costly
and, as of the writing, not always easy to come by. Gas pressure lift systems
are useful in many instances. They are generally light, easy to install, and
can be powered by several different pressure systems, usually compressed
nitrogen or air. The effect of the contact between the pressure gas and the
groundwater usually results in changes in the dissolved gas content. As a
result pH, conductivity, or other analysis used to determine purge completion
must be conducted down hole. Recent developments in the use of pumps powered
by compressed gas have shown promise. Although these too have large gas
volume demands when operated at substantial depths, some versions, such as the
one built and tested by the NCASI,^ can also be used for sample collection.
Peristaltic pumps are widely used for purging of wells with water levels close
to the surface (less than 8 meters). They are reasonably portable, light, and
easily adaptable to ground level monitoring of purge indicator parameters by
attaching a flow-through cell. These pumps require a minimum of down hole
equipment and can easily be cleaned in the field; or the entire tubing
assembly can be changed for each well.
Once the well has been sufficiently purged the actual sampling should
begin as soon as the water level begins to approach its pre-purge level.
Sampling for volatile organics may begin even sooner, before substantial
volatilization begins. If recovery is very slow, it may be necessary to wait
several hours or even until the following day before sufficient volume is
available for all the necessary analyses. In this instance a volatile
organics sample set may be collected soon after completion of the purging
process and a second set with the remaining samples. When a pump is used for
sample collection, its rate should be controlled to closely match the
transmissivity of the formation. Excessive draw down of the well during
sampling may result in nonrepresentative samples due to changes in groundwater
flow.11
Bailers are probably the simplest means of collecting groundwater
samples. They result in a minimum of sample disturbance, if carefully
handled. They can be constructed of noncontaminating materials, and their low
relative cost makes the use of a separate device for each well practical, thus
3-28
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eliminating infield cleaning and cross contamination. Peristaltic pumps can
be used for sampling in most shallow wells. They require a minimum of
down-hole equipment and cross contamination can be eliminated by replacement
of the suction tubing between wells. Gibb^ as well as NCASI° found
little difference between samples withdrawn by a peristaltic pump and those
taken by a bailer. These pumps however are not suitable for the collection of
volatile organics due to possible gas stripping; therefore, their use should
be supplemented by a bailer when sampling includes volatile organic species.
The use of submersible pumps for sample collection is possible provided
they are constructed of suitably noneontaminating materials. They can operate
at depths beyond the capabilities of peristaltic pumps and at which bailing
becomes tedious. The chief drawback, however, is the difficulty of avoiding
cross contamination between wells. These systems are generally too expensive
to allow for several separate units and field decontamination is very
difficult and should properly require solvents which may lead to sample
contamination. Their use, therefore, in multiple well programs, should be
carefully considered against bailers.
In general, gas pressure lift systems should not be used for sample
collection as they have been shown to cause considerable changes in the
groundwater character.
3-29
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METHOD III-7: PURGING WITH A PERISTALTIC PUMP
Discussion
The peristaltic pump as described in the surface water sampling section
Method III-3 can be implemented for the presample purging of groundwater
monitor wells.
Uses
The use of a peristaltic pump for well purging is particularly
advantageous since the same system can later be utilized for sample collection
(see Method 111-10). The application, however, is limited to wells with a
depth of less than approximately 8 meters, due to the limited lift
capabilities of peristaltic action.
Procedures for Use
1. Using clean equipment, sound well for total depth and water level,
then calculate the fluid volume in the casing ("casing volume").
2. Determine depth from casing top to mid-point of screen or well
section open to aquifer. (Consult drillers log or sound for bottom.)
3. If depth to raid-point of screen is in excess of 8 meters, choose
alternate system.
4. Lower intake into the well to a short distance below the water level
and begin water removal. Collect or dispose of purged water in an
acceptable manner. Lower suction intake, as required, to maintain
submergence.
5. Measure rate of discharge frequently. A bucket and stopwatch are
most commonly used.
6. Purge a minimum of two casing volumes or until discharge, pH,
temperature, or conductivity stabilize. See discussion on well
purging in Section III, Groundwater.
7. After pumping, monitor water level recovery. Recovery rate may be
useful in determining sample rate.
3-30
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METHOD III-8: PURGING WITH A GAS PRESSURE DISPLACEMENT SYSTEM
Discussion
A pressure displacement system consists of a chamber equipped with a gas
inlet line, a water discharge line and two check valves (see Figure 14). When
the chamber is lowered into the casing, water floods it from the bottom
through the check valve. Once full, a gas (i.e., nitrogen or air) is forced
into the top of the chamber sufficient to result in the upward displacement of
the water out the discharge tube. The check valve in the bottom prevents
water from being forced back into the casing and the upper check valve
prevents water from flowing back into the chamber when the gas pressure is
released. This cycle can be repeated as necessary until purging is complete.
Uses
The pressure lift system is particularly useful when the well depth is
beyond the capability of a peristaltic pump. The water is displaced up the
discharge tube by the increased gas pressure above the water level. The
potential for increased gas diffusion into the water makes this system
unsuitable for sampling for volatile organic or most pH critical parameters.
Procedures for Use
1. Using clean noneontaminating equipment (i.e., an electronic level
indicator) determine the water level in the well then calculate the
fluid volume in the casing.
2. Determine depth to midpoint of screen or well section open to
aquifer (consult drillers log).
3. Lower displacement chamber until top is just below water level.
4. Attach gas supply line to pressure adjustment valve on cap.
5. Gradually increase gas pressure to maintain discharge flow rate.
6. Measure rate of discharge frequently. A bucket and stopwatch are
usually sufficient.
7. Purge a minimum of two casing volumes or until discharge
characteristics stabilize (see discussion on well purging in
Section III, Groundwater).
8. After pumping, monitor water level recovery. Recovery rate may be
useful in determining sample rate.
Source
U.S. Environmental Protection Agency, "Procedures Manual for Ground Water
Monitoring at Solid Waste Disposal Facilities," EPA-530/SW-611, August
1977.
-------
FROM COMPRESSED
GAS CYLINDER OR
AIR PUMP
QUICK HOSE COUPLER
NEEDLE VALVE
PRESSURE GAUGE
SAMPLE LINE
¥
/
/
/
d •_
1 ^4?
»
3/a" PRESSURE LINE J
nL
n~-1_
•H
"Tfc^
_ ]M
F
Jf
LJi
— \ i iv jMmrut ow i i i-c.
/
/
/
/
/
', ^> &>&
/
/
/
•*•
L
? _i»
J: CHECK VALVE
^ fr, SAMPLER BODY
i __ CHECK VALVE
/.._,„,, _ — WFLI CASING
^
Source: Reference 10.
Figure 14. Gas pressure displacement system.
3-32
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METHOD III-9: SAMPLING MONITOR WELLS WITH A BUCKET TYPE BAILER
Discussion
Bucket type bailers are tall narrow buckets equipped with a check valve
on the bottom. This valve allows water to enter from the bottom as the bailer
is lowered, then prevents its release as the bailer is raised (see Figure 15).
Uses
This device is particularly useful when samples must be recovered from
depths greater than the range (or capability) of suction lift pumps, when
volatile stripping is of concern, or when well casing diameters are too narrow
to accept submersible pumps. It is the method of choice for the collection of
samples which are susceptible to volatile component stripping or degradation
due to the aeration associated with most other recovery systems. Samples can
be recovered with a minimum of aeration if care is taken to gradually lower
the bailer until it contacts the water surface and is then allowed to sink as
it fills. The primary disadvantages of bailers are their limited sample
volume and inability to collect discrete samples from a depth below the water
surface.
Procedures for Use
1. Using clean, noncontaminating equipment, i.e., an electronic level
indicator (avoid indicating paste), determine the water level in the
well, then calculate the fluid volume in the casing.
2. Purge well as per Methods III-7 or III-8.
3. Attach bailer to cable or line for lowering.
4. Lower bailer slowly until it contacts water surface.
5. Allow bailer to sink and fill with a minimum of surface disturbance.
6. Slowly raise bailer to surface. Do not allow bailer line to contact
ground.
7. Tip bailer to allow slow discharge from top to flow gently down the
side of the sample bottle with minimum entry turbulence.
8. Repeat steps 2-5 as needed to acquire sufficient volume.
9. Preserve the sample, if necessary, according to the guidelines in
Appendix A.
10. Check that a Teflon-liner is present in cap if required. Secure the
cap tightly.
3-33
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STAINLESS WIRE
CABLE
J_L
1/4 O.D.x I 1.0. TEFLON
EXTRUDED TUBING,
18 TO 36"LONG
I 3/4 "DIAMETER
GLASS OR TEFLON
_5- l" DIAMETER TEFLON
EXTRUDED ROD
'5/16" DIAMETER
HOLE
Source: Reference 9.
Figure 15. Teflon bailer.
3-34
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11. Label the sample bottle with an appropriate tag. Be sure to
complete the tag with all necessary information. Record the
information in the field logbook and complete all chain-of-custody
documents.
12. Place the properly labeled sample bottle in an appropriate carrying
container maintained at 4°C throughout the sampling and
transportation period.
13. Rinse bailer with deionized water before reuse. In some casesj
especially where trace analysis is desired, it may be prudent to use
a separate bailer for each well or, if possible, to thoroughly
decontaminate the bailer after each use according to specific
laboratory instructions. After use, place in plastic bag for return
to lab.
Sources
Dunlap, W.J., McNabb, J.F., Scalf, M.R. and Crosby, R.L., "Sampling for
Organic Chemicals and Microorganism in the Subsurface." EPA-600/2-77-176,
August 1977.
3-35
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METHOD 111-10: SAMPLING MONITOR WELLS WITH A PERISTALTIC PUMP
Discussion
A pump system is considerably advantageous when analytical requirements
demand sample volumes in excess of several liters. The major drawback of a
pump system is the potential for increased volatile component stripping as a
result of the required lift vacuum. Samples for volatile organic analysis
should be collected with a bailer as described in Method III-9 and should
precede any sample collection which may further disturb the well bore content.
Uses
The peristaltic pump system can be used for monitor well sampling
whenever the lift requirements do not exceed 8 meters. It becomes
particularly important to use a heavy wall tubing in this application in order
to prevent tubing collapse under the high vacuums needed for lifting from
depth.
Procedures for Use
1. Using clean, noncontaminating equipment, i.e., an electronic level
indicator (avoid indicating paste), determine the water level in the
well, then calculate the fluid volume in the casing.
2. Purge well as per Methods III-7 or III-8.
3. If soundings show sufficient level of recovery, prepare pump
system. If insufficient recovery is noted allow additional time to
collect samples on a periodic schedule which will allow recovery
between samplings.
4. Collect volatile organic analysis samples if required with bucket
type bailer (Method III-9) .
5. Install clean medical grade silicon tubing in peristaltic pump head.
6. Attach pump to required length of Teflon suction line and lower to
midpoint of well screen if known or slightly below existing water
level.
7. Consider the first liter of liquid collected as a sample as system
purge/rinse. NOTE: If well yield is insufficient for required
analysis this purge volume may be suitable for some less critical
analysis.
8. Fill necessary sample bottles by allowing pump discharge to flow
gently down the side of bottle with minimal entry turbulence. Cap
each bottle as filled.
9. Preserve the sample if necessary as per guidelines in Appendix A.
3-36
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10. Check that a Teflon-liner is present in cap if required. Secure the
cap tightly.
11. Label the sample bottle with an appropriate tag. Be sure to
complete the tag with all necessary information. Complete
chain-of-custody documents and field log book.
12. Place the properly labeled sample bottle in an appropriate carrying
container maintained at 4°C throughout the sampling and
transportation period.
13. Allow system to drain then disassemble. Return tubing to lab for
decontamination.
Sources
Dunlap, W.J., McNabb, J.F., Scalf, M.R. and Crosby, R.L. "Sampling for
Organic Chemicals and Microorganisms in the Subsurface,"
EPA-600/2-77-176, August 1977.
3-37
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SECTION 4
GASES, VAPORS, AND AEROSOLS
GENERAL
Air monitoring at hazardous waste sites and environmental spills can be
quite useful as an indicator of potential safety problems and as a means of
screening for the presence of possible airborne contaminants. Monitoring is
also important as a means of determining the specific identity and
concentration of airborne toxic and hazardous pollutants onsite and the extent
of their migration offsite. For the purpose of this document, sampling for
gases, vapors and aerosols at hazardous waste sites and environmental spills
falls into three general categories: the ambient atmosphere, soil gases, and
container headspace gases.
AMBIENT
Ambient concentrations of airborne contaminants are greatly affected by
the topography and meteorology of the surrounding area, and the investigator
must be cognizant of this when choosing monitoring methods and equipment.
Besides the obvious effects of temperature, wind, and precipitation in
relation to dispersion and deposition of atmospheric pollutants, heat and
sunlight can dramatically increase rates of volatilization and cold and calm
may cause stagnant conditions to prevail tending to reduce migration and
concentrate pollutants in low-lying areas. Accurate detection of atmospheric
pollutants must take into account these and other factors if a successful
sampling effort is desired.
Of major importance when discussing the sampling of ambient atmospheres
is the use of portable analytical instrumentation. In addition to being
portable, these devices need to be rugged and easy to operate and need to
provide real time data in order to best meet the requirements inherent to
field applications. They must also be proven safe when used in hazardous
waste environments. Electrical devices and instruments which utilize flame or
combustion principles must be of a type that eliminate the possibility of
igniting combustible atmospheres. All instruments used should be "approved"
or "certified" by Underwriters Laboratory (UL) or Factor Mutual Systems (FM)
according to provisions set forth by the National Electrical Code (NEC).
4-1
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In order to insure safe operation, the user must also become familiar
with the detailed operation and maintenance procedures found only in the
specific instrument's operating manual. The investigator should keep in mind
that the procedures outlined here are necessarily general and intended only to
supplement the instrument operating manual. Investigators must also
familiarize themselves with the limitations of each instrument. Inability to
detect certain compounds, insensitivity (e.g., contaminants in the solid
phase), slow response time, pump rate capacity, etc. are all factors which may
affect the safety of the operator and/or quality of the data.
Field instrumentation is invaluable during initial site surveys for
assessing the potential hazards that exist. Information of this nature is
needed in order to determine the degree of protection required for personnel
or to provide direction for further quantification of specific parameters.
Instruments such as portable oxygen indicators and combustible gas
detectors would be the instruments of choice when a general safety assessment
of an unknown atmosphere is necessary. Such atmospheres present many hazards
including oxygen deficiency, explosivity, flammability, etc., and data
obtained with these instruments can be used by the onsite safety officer to
generally assess the presence of these dangers and dictate precautionary
measures to be taken. They can be used to screen pockets or depressions in
the land contour, areas in close proximity to drums or spills, or closed in,
unventilated rooms which may not have enough oxygen to support life or which
allow combustible vapors to concentrate.
Other instruments that are useful for evaluating the hazard potential of
ambient or workplace atmospheres are those which utilize flame ionization
(FID) and photoionization (PID) detectors. These detectors are important due
to the increased levels of sensitivity they can provide (for specific compound
classes) and when used in conjunction with chromatographic columns, can
specifically characterize and/or identify hazardous materials at spills or
dump sites.
The Century OVA and AID Model 550 represent a type of instrumentation
utilizing a flame ionization detector and in its simplest form is used to
determine the presence of gaseous and/or vapor phase hydrocarbons. These
instruments provide a cumulative response to most gaseous/vapor phase organics
present as referenced to a single component standard gas (usually methane).
The response of such instruments is often termed "total hydrocarbons;"
however, this is misleading since not all hydrocarbons are detected,
specifically important particulate hydrocarbons (i.e., pesticides and
polynuclear aromatics), and polychlorinated biphenyls. In addition, the
response to mixtures of vapor phase hydrocarbons depends upon the ratios and
the types of organic compounds present and cannot be related to a specific
vapor concentration. FIDs do, nonetheless, provide a useful and reliable tool
for general assessment purposes.
Photoionization analyzers such as the portable HNU Model Pl-101 are also
capable of detecting the presence of a wide variety of chemical species, both
4-2
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organic and inorganic. As with the FID's, photoionization detectors suffer
similar limitations of detector response to component mixtures and the
inability to respond to certain compounds must be recognized; however, they
also provide important information for evaluation purposes.
As stated previously, the usefulness of both portable FID's and PID's can
be expanded when used in conjunction with chromatography. The Century units
offer a chromatography option which, when used properly, can be quite a
valuable tool for aiding in specific compound identification. At present, the
HNU Pl-101 is not available with a chromatography option; however Spittler and
Oi-*- report success with a portable photoionization detector/gas
chromatograph (Photovac 10A10, Thornhill, Ontario) capable of sensitivity in
the 0.1 to 10 ppb range. In all cases it should be realized that
chromatography can be quite complex and demands the skills of an experienced
operator to obtain valid and meaningful results.
Additional useful instruments and devices include those adapted from
industrial hygiene practices and/or techniques. These include stain detector
tubes and personnel collection devices. Detection by these methods is the
most specific of all of the devices thus far described. These methods are
therefore extremely useful for compound identification and quantification.
Stain detector tubes such as manufactured by National Drager,
Matheson-Kitwgawa, Bendix Corporation, and MSA provide an immediate indicator
of a specific chemical or species of interest. They are somewhat limited due
to small sample volume, interferences, degree of accuracy, operator judgement,
etc.; however, they are valuable as a quick, relatively simple, direct-reading
method of determining specific gas concentrations.
Collection devices such as solid sorbents, chemical absorbing solutions
and filters are the most accurate of the methods used for properly identifying
and quantifying species of interest. Use of these methods requires adherence
to very specific procedures and conditions of the type found in the "NIOSH
Manual of Analytical Methods,"1^ EPA Federal Reference Methods, or specific
papers documenting procedures and characteristics of sorbent resins.
Collected samples are subsequently analyzed at an offsite analytical
laboratory that usually yields an analytical precision and accuracy presently
unavailable in most field applications.
It should be noted, at this point, that ambient monitoring, within the
context of this section, deals with area monitoring and not personnel
monitoring. Although ambient methods can provide information on the types of
contaminants present and the relative magnitude of contamination, it is not a
substitute for personnel monitoring when worker exposure is the prime
concern. In such cases, NIOSH methodologies should be consulted and
appropriate methods chosen dependent upon specific monitoring requirements.
4-3
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METHOD IV-1: DETERMINING OXYGEN CONTENT IN AMBIENT AND WORKPLACE
ENVIRONMENTS WITH A PORTABLE OXYGEN MONITOR
Discussion
A portable oxygen monitor has three principle components for operation.
These include the airflow system, the oxygen sensing device, and the microamp
meter. Air is drawn through the oxygen sensor with a built-in pump or
aspirator bulb. The sensor indicates the oxygen content and the information
is translated electrochemically to the meter.
Most monitors have meters which indicate the oxygen content from 0-25
percent. There are also oxygen monitors available which indicate
concentrations on scales from 0-5 percent and 0-100 percent. The most useful
for ambient measurements is the 0-25 percent oxygen content readout. Many
instruments also have alarm modes which can be set to activate at a specified
oxygen concentration.
Uses
Portable oxygen monitors are invaluable when initially responding to
hazardous material spills or waste site situations. They are useful in
screening depressions in the land, unventilated rooms, or other areas that may
not contain enough oxygen to support life. When used properly the portable
oxygen monitor will indicate the percent oxygen in the test atmosphere.
Normal oxygen concentration required for respiration is 20.9 percent.
Procedures for Use
1. Make sure instrument is clean and servicable, especially sample
lines and detector surfaces.
2. Consult records on instrument maintenance to determine if detector
solution should be changed. Some instruments will need this service
after as little as 1-2 weeks of use.
3. Check battery charge level. If in doubt, charge battery as detailed
in operating manual. Some units have charge level indicators while
others have alarms that will indicate a low charge.
4. Verify (if possible) that sample pump is operable when analyzer is
on.
5. Turn pump on and, using calibration knob on instrument, calibrate
against fresh air (20.9 percent 02) by aligning meter needle at
20. 9 percent.
6. If unit is equipped with alarm mode, set alarm at desired level.
7. Allow for instrument warmup, if necessary, before entering site to
take readings.
4-4
-------
8. Position intake assembly in close proximity to area in question to
get accurate reading.
9. If alarm occurs, personel should evacuate area, unless equipped with
supplied air equipment.
10. Some important factors to keep in mind during use are:
• Slow sweeping motions may assist in the prevention of bypassing
problem areas.
• Operation of instrument in temperatures outside of manufacturer
specified operating range may compromise accuracy of readings
or damage unit.
• Presence of known or unknown interfering gases, especially
oxidants, can affect readings (for example the Edmont Model
60-400 Oxygen Monitor has interferences of the following gases
in concentrations greater than 0.25 percent or 2500 ppm:
S02> fluorine, chlorine, bromide, iodines and nitrogen
oxides). See the operating manual for unit being used.
• The oxygen detector can also be poisoned (decrease in
sensitivity) by exposure to various gases. Some detectors are
poisoned by concentration of mercaptans and hydrogen sulfide
greater than or equal to 1 percent. See operating manual for
unit being used.
• When relying on alarm mode for warnings of oxygen deficient
atmospheres, a manual check of the alarm function at regular
intervals is recommended.
• Wherever applicable, protect instrument with a disposable cover
to prevent contamination.
• Most units will have rechargeable battery packs that provide
continuous operation for 8-12 hours. Recharging batteries
prior to expiration of the specified interval will insure
operation while on a site.
• More than any other factor, effective utilization of unit
requires operator with full understanding of operating
principles and procedures for the specific instrument in use.
Sources
Edmont Model 60-400 Combustible Gas/Oxygen Monitor Instruction Manual.
Manufactured by Energetics Science, Elmsford, NY 10523.
U.S. Environmental Protection Agency. "Hazardous Materials Response
Operations Training Manual." National Training and Operational Center,
Cincinnati, OH.
4-5
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METHOD IV-2: DETERMINATION OF COMBUSTIBLE GAS LEVELS USING A
PORTABLE COMBUSTIBLE GAS INDICATOR
Discussion
A combustible gas indicator has three major operational components: air
flow system, combustion filament, and ohmmeter. Simply stated, the sample gas
is drawn into the unit through a sample line and into the combustion chamber.
In the combustion chamber the detector consists of a platinum filament whose
resistance is dependent on its temperature. As the sample gas is combusted,
changes in the resistance of the filament are measured directly by the
ohmmeter as the ratio of combustible gas present to the total required to
reach the lower explosive limit (LEL).
The lower explosive limit or LEL (also LFL, lower flammability limit) is
defined as the lowest concentration of gas in air which can be ignited by an
ignition source and cause an explosion. Conversely, the upper explosive limit
or UEL (also UFL, upper flammability limit) is the concentration of gas in air
above which there is insufficient oxygen available to support combustion,
therefore, no explosion is possible. In general, the instruments respond in
the following manner:
• The meter indicates 0.5 LEL (50 percent). This means that 50
percent of the concentration of combustible gas needed to reach an
unstable combustible situation is present. If the LEL of the gas is
5 percent, then the instrument indicates a 2.5 percent mixture is
present.
• The meter needle stays above 1.0 LEL (100 percent). This means that
the concentration of combustible gas is greater than the LEL and
less than the UEL and, therefore, immediately combustible and
explosive.
• The meter needle rises above the 1.0 (100 percent) mark and then
returns to zero. This response indicates the ambient atmosphere has
a combustible gas concentration greater than the UEL.
Of the many instruments commercially available for detecting combustible
or explosive gas, some are not certified safe for operation in the atmospheres
they can detect. It is important to use only those monitors that are
certified safe for use in atmospheres greater than 25 percent of the LEL.
Organizations that perform this certification are the Mine Safety and Health
Administration (MSHA), Underwriters Laboratory (UL), and Factory Mutual (FM).
Some combustible gas monitors provide readouts in units of percent LEL,
some in percent combustible gases by volume, and some have scales for both.
Many situations may occur where the types of combustible gases to be
encountered are unknown. In such instances, a meter calibrated to provide
readings in units of percent LEL of methane will provide a more sensitive
indication of the explosivity of the sample gas and thus provide a margin for
4-6
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error. The operator should be familiar with the LEL concentrations for
specific gases to effectively utilize a unit providing data in percent
combustibles (by volume) only.
Although monitors can be purchased that are factory calibrated using
gases such as butane, pentane, natural gas, or petroleum vapors, methane
calibration is normally used and completely satisfactory for use in ambient
atmospheres. The LEL of methane is 5 percent by volume in air, therefore, an
air mixture containing 5 percent methane will be read as 100 percent LEL and
will be explosive if a source of ignition is present. When combustible gases
other than methane are sampled, the relative response of the detector for
these other gases must be considered. The sensitivity of the detector and the
lower explosive limit differences will produce varying meter responses in
terms of percent LEL for the same concentrations. Actual correlation
equations that will convert the percent LEL (based on methane) read by the
unit to a percent LEL for another combustible gas can usually be found in the
operating manual.
Most units also have alarm systems which can be adjusted for various
LEL1s and several are available that incorporate oxygen analyzers.
Uses
In general, combustible gas detectors are used to determine the potential
for combustion or explosion of unknown atmospheres. These instruments, in
combination with oxygen detectors and radiation survey instrumentation, should
be the first monitors used when entering a hazardous area. In this sense they
provide a general indication of the degree of immediate hazard to personnel
and can be used to assist the safety officer in making decisions on levels of
protection required at the site.
Procedure for Use
1. Make sure instrument is clean and serviceable, especially sample
lines and detector surfaces.
2. Check battery charge level. If in doubt, charge battery as
described in operating manual. Some units have charge level meters,
while others have only low charge alarms.
3. Turn unit to ON position, and allow instrument sufficient warmup
time.
4. Verify (if possible) that sample pump is operable when analyzer is
ON.
5. With the intake assembly in gas-free ambient air, zero the meter by
rotating the zero control until the meter reads 0 percent LEL.
6. Calibrate unit against known concentration of methane by rotating
the calibration control until the meter reads the same concentration
as the known standard.
4-7
-------
7. If necessary, adjust alarm setting to appropriate combustibility
setting.
8. Position intake assembly in close proximity to area in question to
get accurate reading.
9. If alarm occurs, personnel should evacuate area.
10. If instrument malfunction occurs, personnel should evacuate area.
11. Some important factors to keep in mind during use are:
• Slow sweeping motions of intake assembly will help assure that
problem atmospheres are not bypassed.
• Operation of unit in temperatures outside of recommended
operating range may compromise accuracy of readings or damage
the instrument.
• Platinum filament detectors will be poisoned (reduced in
sensitivity) by gases such as leaded gasoline vapors
(tetraethyl lead) and sulfur compounds (mercaptans and hydrogen
sulfide).
• Many combustible gas detectors are not designed for use in
oxygen-enriched atmospheres. If this condition is encountered
or suspected, personnel should evacuate the area. Specially
designed units are available for operation in such atmospheres.
• Unless a charcoal filter is employed prior to the detector
there is no distinction between petroleum vapors and
combustible gases.
• Accurate data depends on regular calibration and battery
charging. See operating manual.
• More than any other factor, effective utilization of unit
requires operator with full understanding of operating
principles and procedures for the specific instrument in use.
Sources
Edmont Model 60-400 Combustible Gas/Oxygen Monitor Instruction Manual,
Manufactured by Energetics Science, Elmsford, NY 10523.
U.S. Environmental Protection Agency. "Hazardous Materials Incident
Response Operators Training Manual." National Training and Operational
Training Center, Cincinnati, Ohio.
4-8
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METHOD IV-3: MONITORING ORGANIC VAPORS USING A PORTABLE FLAME IONIZATION
DETECTOR
Discussion
A flame ionization detector (FID) will respond to most organic vapors as
they form positively charged ions when combusted in a hydrogen flame. The
magnitude of the response is a function of the detector sensitivity and the
ionization properties of the particular compound as well as its
concentration. As a result, this signal must be compared to that generated by
calibration with a known concentration of a standard gas. The sample
concentration is then reported as the ppm equivalent of the calibration
compound. Most units are calibrated with a known concentration of methane;
however, almost any gaseous hydrocarbon that produces a response can be used.
Many models also have built-in calibration circuits which can insure that the
electronic response to a known signal remains constant.
Some models can be equipped with an option that will allow for the
chromatographic separation of the sample gas constituents. This allows for a
tentative qualification and quantification of the resultant peaks which have
retention times equal to those of known standards. This option requires the
use of a chart recorder for recording the peak areas and retention times and,
in such a mode, prevents the instrument from providing a continuous readout.
Use of a chromatographic option also requires additional expertise if reliable,
consistent results are desired.
Most portable FID's rely on the sample gas to supply the combustion air
to the detector flame, so they are designed to operate in ambient atmospheres
with relatively normal oxygen concentrations (21 percent). This design
precludes the sampling of process vents, poorly ventilated or sealed
containers, or any sample gas hydrocarbon concentration sufficient to reduce
the available oxygen or otherwise saturate the detector. In such instances
adaptations are usually available to supply a source of oxygen from a
compressed gas bottle or introduce the gas through a dilution system with a
known (calibrated) dilution factor.
Uses
A portable FID is useful as a general screening tool to detect the
presence of most organic vapors. It will not, however, respond to particulate
hydrocarbons such as pesticides, PNAs and PCBs. It can be used to detect
pockets of gaseous hydrocarbons in depressions or confined spaces, screen
drums or other containers for the presence of entrapped vapors, or generally
assess an area for the presence of elevated levels of vapor phase organics.
Procedure for Use
The procedures presented in this section are intended to apply to any
portable FID; therefore, detailed operating instructions must be obtained from
the operating manual of the specific unit to be used.
4-9
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1. Check battery charge level indicator; if in doubt, recharge battery
as described in manual.
2. Turn instrument on and allow adequate warmup time.
3. If equipped with internal calibration capability, perform instrument
calibration. Perform zero and other calibration procedures as
described in operating manual.
4. If equipped with an alarm mode, set alarm at desired concentration.
5. Turn on pump and leak check by covering sample inlet and observing
rotameter. Indicator ball should drop to zero level.
6. With pump operating, open hydrogen gas storage tank valve and open
supply regulator to allow fuel gas flow to detector chamber.
7. Depress igniter switch, observe indicator needle for positive
response and listen for a "pop." If flame fails to light, depress
ignite switch again.
8. Once detector flame is lit, unit is ready for use.
9. If calibration to a specific hydrocarbon species is desired,
complete this procedure as per the manufacturers instructions.
10. Hold sample probe in close proximity to area in question as low
sample rate allows for only very localized readings.
11. Slow sweeping motion will help prevent the bypassing of problem
areas. Make sure batteries are recharged within time frame
specified in operator manual. Usual length of operating time
between charges is 8-12 hours.
11. Some units have alarms that signal operator if detector flame goes
out. If this alarm sounds, evacuate all personnel and relight flame
in known safe area then reenter site.
12. Monitor fuel and/or combustion air supply gauges regularly to insure
sufficient gas supplies.
13. High background readings after prolonged use may indicate sample
probe and/or in-line filters (prior to detector) need to be
cleaned. Use of pipe cleaners or clean air blown backwards through
filters is adequate. Do not use organic solvents as detector will
respond to solvent as well.
14. Representative readings will also depend on performance of routine
maintenance as described in detail in operating manual. Also, since
unit contains pressurized gas supplies, perform leak check procedures
regularly, as leaking hydrogen gas is explosive.
4-10
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15. As with any field instrument accurate results depend on the operator
being completely familiar with the operator's manual for the
particular unit.
16. Concentrations beyond the greatest scale factor of the instrument or
in excess of 30 percent (0.3) LEL of the sample component require
system modification. Similar requirements are the result of
sampling in oxygen-deficient atmospheres. This usually entails
increasing the combustion air to the detector by sample dilution or
by an independent air supply. A dilution system is simply the
apparatus required to supply a filtered controlled air supply for
analyzers that utilize a sample gas stream as the carrier gas,
combustion air and the sample. A dilution system can, by selection
of various critical orifices, dilute a gas stream by ratios up to
100:1.
17. Always be sure that carrier gas flow (usually sample gas) is
initiated prior to lighting the detector flame.
Sources
Analabs, A Unit of Foxboro Analytical. "Operating and Service Manual for
Century Systems' Portable Organic Vapor Analyzer (OVA) Model OVA-108 and
Optional Accessories, Revision C," North Haven, Connecticut.
4-11
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METHOD IV-4: MONITORING TOXIC GASES AND VAPORS USING A PHOTOIONIZATION
DETECTOR
Discussion
This method is designed to detect, measure and record real-time levels of
many organic and inorganic vapors in air. A photoionization detector (PID)
will respond to most vaporous compounds in air that have an ionization
potential less than or equal to that supplied by the ionizing source in the
detector, an ultraviolet lamp. The magnitude of this response is a function
of the detector sensitivity and the concentration and ionization properties of
the individual compound. Though it can be calibrated to a particular
compound, the instrument cannot distinguish between detectable compounds in a
gaseous matrix and therefore indicates an integrated response in relation to
the response factors of all ionizable species present.
The analyzer employs the principle of photoionization for detection.
This process is termed photoionization since the absorption of ultraviolet
light (a photon) by a molecule leads to ionization via:
RH + hv = RH+ + e~
where RH = trace gas,
hv = a photon with an energy _> Ionization Potential of RH
The sensor consists of a sealed ultraviolet light source that emits
photons which are energetic enough to ionize many trace species (particularly
organics) but do not ionize the major components of air such as 02> N2,
CO, C02, or H20. A chamber adjacent to the ultraviolet source contains a
pair of electrodes. When a positive potential is applied to one electrode,
the field created drives any ions, formed by absorption of UV light, to the
collector electrode where the current (proportional to concentration) is
measured. This signal is amplified and conditioned and then sent to the
output display.
To minimize adsorption of various sample gases, the ion chamber is
usually made of an inert fluorocarbon material. The sample line is kept as
short as possible, and a rapid flow of sample gas is maintained through the
ion chamber volume.
Uses
The portable photoionization detector is useful as a general survey
instrument at waste sites and hazardous material spills. As such, it is
similar to an FID in application; however, its capabilities are somewhat
broader in that it can detect certain inorganic vapors. Conversely, the PID
is unable to respond to certain low molecular weight hydrocarbons (e.g.,
methane and ethane) that are readily detected by FID.
4-12
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Procedure for Use
The procedural steps delineated herein are by design general. The
operating manual for the unit being used should be consulted for specific
instructions.
1. Check battery charge level. If in doubt, charge battery as
described in manual.
2. Turn unit on. Verification of UV lamp operation can be made by
looking into sensor for purple glow of the lamp.
3. Perform zero and calibration procedure as described in operating
manual. Calibration for specific compounds can be performed so that
instrument response is proportional to the calibration gas
concentration.
4. If so equipped, set alarm at desired level.
5. Once calibrated, unit is ready for use.
6. Position intake assembly in close proximity to area in question as
sampling rate allows for only very localized readings.
7. A slow sweeping motion of intake assembly will help prevent the
by-passing of problem areas.
8. Be prepared to evacuate the area if preset alarm sounds. Operators
utilizing supplied air systems may not need to consider this action.
9. Static voltage sources such as AC power lines, radio transmissions,
or transformers may interfere with measurements. See operating
manual for discussion of necessary considerations.
10. Regular cleaning and maintenance of instrument and accessories will
assure representative readings.
11. As with any field instrument, accurate results depend on the
operator being completely familiar with the operator's manual for
the unit in use.
Sources
HNU Systems Inc. "Instruction Manual for Model PI 101 Photoionization
Analyzer." 1975.
4-13
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METHOD IV-5: STAIN DETECTOR TUBE METHOD FOR SAMPLING GASEOUS COMPOUNDS
Discussion
A relatively simple method for determining concentrations of specific
gaseous pollutants is through the use of stain detector tubes. They are
usually calibrated in ppm for easy interpretation and are either direct
reading or referenced to a supplied concentration or color change chart. The
limiting factors in the application of this methodology are the small variety
of compounds for which detector tubes are available, interfering agents and
cross-sensitivities, short sampling time, and the extremely small sample
volume used. Most detector tubes are species-specific; however, some detect
groups of compounds, e.g., "total hydrocarbons."
The detector tubes are specific for individual compounds and require
specific sampling techniques. This information is supplied with the tubes and
details the required sample volume, proper tube preparation and insertion into
the pump as well as a discussion of the applicability and limitations of the
tube. In general the tubes are opened by snapping off the tips on either end
and inserting them into the pump so the arrow on the tube indicating flow
points toward the pump. The required sample volume is then pulled through the
tube. An indicator chemical in the tube will demonstrate a color change, the
length of which is proportional to the concentration of the compound in
question.
The detector tube and pump are the two major components of the system.
Pumps used for drawing air through the tubes come in two basic forms: bellows
pump and piston-type (syringe). These pumps are manufactured under strict
specifications so as to draw only a specified volume of gas and are designed
to be used with tubes of the same manufacturer.
Uses
Stain detector tubes are useful for screening sources to verify the
presence of suspected compounds and subsequently allow for a sufficient degree
of quantification. They are generally inadequate for ambient air sampling
applications due to the low sample volumes collected. They are more useful
for detection of compounds at higher levels such as in drums, confined work
areas, pockets or depressions, etc.
Procedure for Use
Perform necessary pump leak check procedures. This is usually
accomplished by plugging pump inlet, drawing a vacuum on the pump,
holding it for at least 1 minute and determining visually if leak
allows bellows to inflate or piston fails to return completely into
pump. The pump can be plugged using a sealed detector tube.
4-14
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2. Break open both ends of detector tube, insert correct end into pump,
and sample according to instructions. Most tubes have some kind of
indicator (i.e., arrow, prefilter) that helps determine which end of
tube is the inlet. The direction of the concentration scale is also
a guide.
3. Visually inspect tube for color changes and record corresponding gas
concentration.
4. Additional Notes
• Some tube manufacturers advise that tubes showing negative
results can be reused before they are rendered useless. The
error potential and risk associated with reusing a previously
opened tube is not advisable when working with hazardous
materials.
• Some types of detector tubes have reagent ampules which must be
broken to activate the indicator. Also, some procedures call
for use of multiple tubes, in series for multiple parameter
detection, or specific interference removal.
• The standard range of measurement or the detector sensitivity
can usually be extended by changing the number of pump volumes
pulled through the tube. The upper range limit can be extended
by decreasing the number of pump volumes, and the lower range
limit can be extended by increasing the number of pump volumes.
• Tubes and pumps of different manufacturers should not be used
interehangably. For example, Drager tubes should be used only
with Drager pumps.
Sources
Dragerwerk Ag Lubeck. "Detector Tube Handbook, Air Investigations and
Technical Gas Analysis with Drager Tubes." 4th Edition, August 1979.
Matheson Safety Products. Operating Instructions for Matheson-Kitagawa
Detector Tubes, Matheson Gas Products Model 8014 - Toxic Gas Detector.
4-15
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METHOD IV-6: SAMPLING FOR VOLATILE ORGANICS IN AMBIENT AIR USING SOLID
SORBENTS
Discussion
Solid sorbent cartridges can be used quite successfully to collect
samples of volatile organics in ambient air and workplace environments. The
sample apparatus consists of a sampling cartridge packed with a solid sorbent
of desirable characteristics (e.g., Tenax-GC, activated charcoal, XAD-2) and a
pump system capable of maintaining a constant flow rate across the collection
media for a specified period of time.
In principle, organic vapors present in the air are adsorbed on the
collection media and subsequently either thermally or chemically desorbed in
the laboratory. An aliquot of the desorbed sample is then subjected to
chromatographic analysis (either capillary or packed column) followed by flame
ionization or mass spectrometric detection.
At present, Tenax-GC is the preferred sorbent for sampling volatile
organics in ambient air. ^ It is hydrophobic and thermally stable up to
360°C, and permits thermal desorbtion of volatile organics beyond n-eicosane
at a temperature of 280°C.-'-° Glass or glass-lined stainless-steel sampling
cartridges of various sizes and configurations are available and can be
purchased prepacked or packed to specifications in the laboratory. In any
case, the sorbent and/or prepacked tubes must be thoroughly precleaned and
conditioned prior to use. A recommended procedure involves precleaning a
batch of Tenax by Soxhlet extraction in methanol first, and then pentane for
24 hours each. The sorbent is then oven dried, packed in tubes and
conditioned under carrier gas flow at 250°C (desorbtion conditions) for 2
hours. The conditioning step is conducted twice and as a precaution can be
performed a final time (1 hour run) just prior to use.
Other sorbents or combination of sorbents may be applied with equal
success depending upon the nature of the ambient environment and the specific
species of volatiles under investigation. Monsanto Research Corporation
reports success with a combination sorbent system based on Tenax-GC,
Porapak R, and Ambersorb XE-340 which has been used to collect a broad range
of organic compounds. ' NIOSH procedures may also be used and the "NIOSH
Manual of Analytical Methods"-^ should be consulted where applicable.
Finally, if the detection of specific organics is desired, the characteristics
of the compound and sorbent of interest should be researched-"- ' > ^ and all
sampling parameters adjusted to meet these criteria.
Sorbent cartridges should be stored in Teflon-capped culture tubes prior
to sampling and during shipment to the laboratory. Culture tubes should also
be wrapped in foil to limit exposure of sampling cartridges to UV light.
Analysis should be instituted as quickly as possible in order to prevent
sample degradation. Schlitt, et al., recommend a storage time of 48
hours; however, this is somewhat impractical and a maximum storage period of
r\ i ry f\ l~f
30 days has been used successfully in a previous study. L> In any event,
sorbent cartridges should be stored at 4°C during transport and storage.
4-16
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Personal monitoring pumps are available from a number of vendors and
range in sophistication (and, accordingly, price) from very simple models to
programmable ones capable of compensating for increasing pressure differential
in addition to other features. Care should be taken to select a pump capable
of operating in the desired flow rate range and which has features most likely
to be used by the investigator.
The outlined procedure utilizes a borosilicate glass tube, outside
diameter 16 mm (5/8") by 10 cm in length. The tube is packed with 1.2 grams
of Tenax-GC sorbent with a plug of glass wool at each end (double plug at
inlet). The personal monitoring pumps can be any low-flow model capable of
maintaining an approximate flow rate of 35 cm /minute.
n
This nominal flow rate of 35 cm /minute is maintained across the
sorbent for 12 hours. Slightly higher flow rates and shorter time periods can
be used; however, the total volume sampled in any case should not exceed 25
liters.
Uses
The procedure outlined below utilizes a Tenax-GC packed sampling
cartridge and a pump system capable of maintaining the desired flow rate for
the specified sampling period and is particularly useful for general
qualitative screening of ambient atmospheres for volatile organics. It is
based on a procedure which was used successfully for qualitative and
quantitative analysis of the volatile species listed in Table 1. •"•» A
brief review of the literature^' 23,24,25, 26, 27 reveais that a number of
additional compounds (Table 2) have been analyzed either qualitatively or
quantitatively using modifications of the procedure described herein. It
should be noted, however, that since the compounds listed in Table 2 are taken
from literature applications of similar methods, testing or further review
should be performed to perfect and prove the method for these compounds prior
to actual sampling and analysis.
Procedures for Use
1. Calibration Procedure*
a. Select a set of sample pumps and assemble necessary equipment
(see Figure 16).
b. Measure ambient air temperature, relative humidity, and
barometric pressure. Determine water vapor pressure from
tables and adjust vapor pressure dependent upon relative
humidity.
*This procedure does not take into account personal monitoring pumps with
pressure compensation and programmable timers. If these are being used,
refer to the manufacturers' instructions for calibration.
4-17
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TABLE 1. VOLATILE ORGANICS COLLECTED WITH A TENAX SORBENT SAMPLING
SYSTEM USING PARAMETERS OUTLINED IN METHOD IV-621'22
Quantitative Analysis
Benzene
Carbon tetrachloride
Chlorobenzene
o-Chlorotoluene
p-Chlorotoluene
1,2-Dibromoethane
o-Dichlorobenzene
p-Dichlorobenzene
1,1,2,2-Tetrachloroethylene
Toluene
Qualitative Analysis
Chloroform
1,2-Dichloroethane
2,4-Dichlorotoluene
o-Chlorobenzaldehyde
p-Chlorobenzaldehyde
Benzyl Chloride (a-chlorotoluene)
1,1-Dichloroethane
1,1-Dichloroethylene (vinylidene chloride)
1,2-Dichloroethylene
Dichloromethane
Phenol
o-Xylene
m-Xylene
p-Xylene
4-18
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TABLE 2. LITERATURE SUMMARY - VOLATILE ORGANICS AMENABLE
TO COLLECTION BY TENAX SORBENT CARTRIDGES
Component Reference(s)
N-Nitroso dimethyl amine
fc-Propio lac tone
Ethyl methansulfonate
Nitromethane
Glycidaldehyde
Butadiene diepoxide
Styrene Epoxide
Aniline
Bis (chloromethyl) ether
Bis (2-chloromethyl) ether
Diethyl Sulfate
Acrolein
Propylene Oxide
Cyclohexene Oxide
Styrene Oxide
Ac e t op he none
1,2-Dibromo methane
1,2-Dichloro ethane
Methanol
Ethanol
Propanol
Ethyl Acetate
Acetone
1, 2,4-Trichlorobenzene
1,2,3, 5-Tetrachlorobenzene
Pentachlorobenzene
Hexachlorobenzene
23
23
23
23
23
23
23
23
23
23
24
24
24
24
24
24, 16
25
25
26
26
26
26
26, 16
27
27
27
27
(continued)
4-19
-------
TABLE 2 (continued)
Component
ReferenceC s)
Bromoform
1,2-Dibromomethane
Phenol
p-Chlorophenol
2,4,6-Trichlorophenol
Diphenyl Oxide
o-Phenyl phenol
Pentachlorophenol
n-Pentane
2-Methyl pentane
3-Methyl pentane
n-Hexane
Heptane
Trichloroethylene
n-Octane
Ethylbenzene
n-Nonane
Benzaldehyde
Propylbenzene
Trimethylbenzene
o-Ethyl toluene
27
27
27
27
27
27
27
27
16
16
16
16
16
16
16
16
16
16
16
16
16
4-20
-------
i
N>
GRADUATED
BURETTE
SOAP
SOLUTION
•D=
D
TUBING
SORBENT
CARTRIDGE
.SAMPLING PUMP
ROTAMETER
Figure 16. Schematic of calibration system.
-------
If battery test is available, check battery.
Place sorbent cartridge in line and start pump. Allow pump to
stabilize.
Determine flow rate with bubble tube flow meter. Use the
following equation to correct for Standard Temperature and
Pressure.
Bubble Tube
Volume (cc)
Travel Time
(min)
P - P T
F V S
p T
S F
STP Flow Rate =
whe re :
Pp = atmospheric pressure (in Hg)
Py = water vapor pressure at calibration temperature and relative
humidity (in Hg)
Pg = standard atmospheric pressure (29.92 in Hg)
Tg = standard temperature (273°K)
Tp = ambient temperature of calibration (°K)
f. Adjust sampler flow rate to approximately 35 cm^/min.
Verify that flow rate has been achieved by checking against
bubble tube three times. Calculate STP flow rates and
calculate a mean value for the three readings (deviation
should not exceed 5%).
g. Mark level on rotameter (if present) for reference.
2. Sampling Procedure
a. Assemble sampling train. The train shown in Figure 17 is
useful if breakthrough determinations are desired; however a
sampling train with only a single cartridge could be used for
qualitative determinations. Set train up at sampling
location. A tripod, music stand, or similar device can be used
to hang the sampler.
b. Record all initial information (time, counter reading,
cartridge number, pump number, sampler, blank number, etc).
c. Start pump and observe rotameter (if present) to determine if
desired flow rate is being maintained. Adjust if necessary.
d. Periodically check pump to determine if flow rates are being
maintained. Adjust if necessary.
4-22
-------
GLASS WOOL GLASS WOOL
INLET-
TENAX-GC
\
TENAX-GC
TUBING
SAMPLING
PUMP
O
Figure 17. Schematic of Tenax sampling train using backup cartridge.
-------
e. Allow pump to run for twelve (12) hours. A shorter sampling
time and slightly higher flow rate can be used as long as the
total volume sampled does not exceed 25 liters.
f. Determine final flow rate by observing rotameter. If a more
accurate determination is desired, recheck flowrate with a
bubble tube as described under Calibration Procedures. If
flowrate has changed by ^5 percent, note in field log.
g. Shut off sampling pump and record all information at end of
sampling period (counter reading, time, barometric pressure,
problems).
h. Remove Tenax cartridges and place into clean culture tubes.
Use caution when handling tubes. If possible wear clean nylon
gloves. Make sure to label which tube was first and which was
backup.
i. Place chain-of-custody tag on sample container and fill out
chain-of-custody log.
j. Store sample at 4°C and protect from sunlight prior to shipment
to the laboratory.
Sources
GCA Corporation. "Quality Assurance Plan, Love Canal Study, Appendix A,
Sampling Procedures." EPA Contract 68-02-3168.
GCA Corporation. "Quality Assurance Plan, Love Canal Study, Appendix B,
Analytical Procedures." EPA Contract 68-02-3168.
GCA Corporation. "Guidelines for Air Monitoring at Hazardous Waste
Sites - Draft." EPA Contract 68-02-3168. May 1982.
4-24
-------
METHOD IV-7: COLLECTING SEMIVOLATILE ORGANIC COMPOUNDS USING
POLYURETHANE FOAM
Description
Polyurethane foam (PUF) has been shown to be an excellent collection
medium for trapping a variety of semivolatile organic compounds. Foam plugs
are cut from the type of PUF used for furniture upholstery, pillows, and
mattresses and Soxhlet extracted with high grade hexane (pesticide quality or
equivalent) prior to being fitted into specialized sampling cartridges. A
known volume of air is drawn through the collection media to trap the airborne
organics.
Cylindrical polyurethane foam plugs (polyether type, 0.021 gm/cm3) are
cut from 3-inch stock using a 25 mm circular template. The soxhlet extracted
plugs are then placed (under slight compression) in 22 mm (inside diameter) by
10 cm long hexane rinsed glass tubes. The glass tubes are constructed from 22
mm (inside diameter) stock which has been tapered at one end to facilitate
attachment to the sampling pump. A teflon reducing adaptor can also be
fabricated which permits attachment to the sampling pump with no modification
to the glass tube.
Any high-volume personnel sampling pump capable of maintaining a constant
flow rate of 3 to 4 j.iter/minute can be used. Samples are collected at this
nominal flow rate for between 8 to 12 hours allowing a total sample volume of
between 1 to 4 cubic meters (m ).
Polyurethane foam has been shown to be excellent for trapping a wide
variety of semivolatile organic compounds in ambient air including numerous
98 yQ "}fl "^1
chlorinated pesticides, '»' polychlorinated biphenyls
(PCBs),28'29'30'32 polychlorinated naphthalenes,29 herbicides30'33 and
"\0 ^{^ 9Q ^f)
their corresponding methyl esters, >J organophosphorus pesticides, 3»
chlorinated benzenes, chlorinated phenols, ° and polynuclear aromatic
hydrocarbons. '^ Table 3 lists the representative components of the above
compound classes that have been collected in ambient air using this technique.
Uses
This procedure and modifications of this procedure have been used
successfully to collect airborne chlorinated organics including pesticides,
PCBs, and a variety of chlorinated benzenes and phenols and is generally
applicable to the measurement of such compounds in the ng/m3 to yg/m3
range when sensitive analytical techniques are employed (GC/Electron
Capture). These methods are generally not applicable for volatile organics in
ambient air nor are they applicable for differentiating between vapor phase
organics and those adsorbed on particulate matter. When collection of such
compounds is desired, it will be necessary to utilize separate collection
media (Tenax-GC, filters, etc.) or combination cartridges. Lewis and
MacLeod describe a combination cartridge which includes a prefilter
(particulates) and a sampling cartridge packed with a PUF or PUF/Tenax
"sandwich" which may be useful for multiple species screening applications.
4-25
-------
TABLE 3. ORGANICS COLLECTED IN AMBIENT AIR USING PUF PROCEDURES
Polychlorinated Biphenyls (PCBs)
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
Chlorinated Pesticides
Chlordane (cis, trans)
Heptachlor
DDE
Dieldrin
p,p'-DDE
p,p'-DDT
o,p'-DDT
a-BHD
Y-BHC (Lindane)
Hexachlorobenzene
Toxaphene
Endrin
Endosulfan I
Aldrin
Mirex
Organophosphorus Pesticides
Diazinon
Methyl Parathion
Malathion
Parathion
Ethyl Parathion
Dichlorvos
Ronne1
Chlorpyrifos
Herbicides
2,4-D esters
Isopropy1
Butyl
Isobutyl
Isooctyl
2,4,5-T N-butyl ester
Broraoxynil
Triallate
Trifluralin
Polynuclear Aromatic Hydrocarbons (PAHs)
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benz(e)acenaphthylene
Polychlorinated Naphthalenes
Halowax 1001
Halowax 1013
Chlorinated Benzenes
1,2,3-trichlorobenzene
1,2,3,4-tetrachlorobenzene
Pentachlorobenzene
1,3,5-trichlorobenzene
Pentachloronitrobenzene
Chlorinated Phenols
2,4-dichlorophenol
2,4,6-trichlorophenol
Pentachlorophenol
2,4,5-trichlorophenol
4-26
-------
The investigator should keep in mind that the procedure described herein is
meant, in its broadest application, to be a screening technique and is
therefore necessarily general. If specific conditions, compounds of interest,
concentrations, detection requirements, etc. are known, such factors should be
carefully considered and the appropriate literature sources reviewed to allow
for procedure optimization relevant to specific needs.
Procedures for Use
1. Calibrate the sampling pump as per the procedure outlined in Method
IV-6. Adjust to a target flow rate of 3 to 4 liters/minute.
2. Sampling procedures
a. Assemble sampling train (see Figure 18). Set train up at
location and hang sampler on a tripod, music stand, or similar
device.
b. Record all initial information (time, counter reading,
cartridge number, pump number, .sampler, blank number, etc).
c. Start pump and observe rotameter (if present) to determine if
appropriate flow rate is being maintained.
d. Periodically check pump to determine if flow rates are being
maintained. Adjust if necessary.
e. Allow pump to run for desired time period (8 to 12 hours).
f. Determine final flow rate by observing rotameter. If a more
accurate determination is desired, recheck flow rate with a
bubble tube as described under Calibration Procedure in Method
IV-6. If flow rate has changed by _^5 percent, note in field
log.
g. Shut down sampling pump and record all information at end of
sampling period (counter reading, time, barometric pressure,
problems).
h. Remove PUF cartridge (use clean plastic or latex gloves) and
cover with hexane rinsed aluminum foil.
i. Place foil-covered cartridge in hexane rinsed glass bottle that
has been properly labeled.
j. Place chain-of-custody tag on sample and fill out chain-of-
custody log.
k. Refrigerate samples prior to and during shipment to the
laboratory.
4-27
-------
GLASS CARTRIDGE
POLYURETHANE FOAM
10
CO
-TUBING
SAMPLING
PUMP
Figure 18. Schematic of Polyurethane Foam (PUF) sampling train for
collection of chlorinated pesticides and PCBs.
-------
Sources
GCA Corporation. "Quality Assurance Plan, Love Canal Study, Appendix A,
Sampling Procedures." EPA Contract 68-02-3168.
Lewis, Robert G. and MacLeod, Kathryn E. "Portable Sampler for
Pesticides and Semivolatile Industrial Organic Chemicals in Air."
Analytical Chemistry, Volume 54, pp. 310-315, 1982.
4-29
-------
METHOD IV-8: DETERMINATION OF TOTAL SUSPENDED PARTICULATE IN AMBIENT AIR USING
HIGH-VOLUME SAMPLING TECHNIQUE
Description
Ambient air is drawn into a covered housing and through a filter by means
of a high-volume blower at flow rates between 1.13 to 1.70 m^/min (40 to 60
ft /min). Particles within the size range of 100 to 0.1 ym diameter are
collected on the filter although sampler flow rate and geometry tends to
favor particles less than 60 ym aerodynamic diameter. The mass concentration
of suspended particulate is computed by measuring the mass of collected
particulates (gravimetric analysis) and the volume of air sampled.
High volume ambient air samplers (Figures 19 and 20) are readily
available from a number of vendors and should meet the specifications
described in 40 CFR Part 50 Appendix B—Reference Method for the Determination
of Suspended Particulates in the Atmosphere (High Volume Method). -* Filter
media (glass fiber filters) with a collection efficiency of at least 99
percent for particles of 0.3 m diameter are also specified for use. Other
types of filter media (e.g., paper) or specially prepared filters may be
desired in instances where specific analysis is contemplated or low background
levels of certain pollutants is desired.
After sample collection, pretared filters are analyzed gravimetrically to
determine the total particulate loading. Trace metal analyses may be
accomplished by extracting all or part of the filter and analyzing the extract
accordingly (i.e., atomic absorbtion, ICP). It should be noted that when
trace metal analysis is desired, it is extremely important to submit blank
filters from each lot to the laboratory to determine background concentrations.
Modified high-volume sampling techniques have also been used to
efficiently collect certain organic compounds. Stratton, et al., and
Jackson and Lewis describe samplers modified to include a throat extension
between the filter housing and blower that contains polyurethane foam
sorbent. This arrangement can also be used to trap polynuclear aromatic
hydrocarbon (PNAs). Additional sorbents or combinations can be used dependent
upon specific collection requirements. As with trace metal analysis, it is
important that blank filters and sorbents be submitted to the laboratory to
determine the existence of background concentrations.
Uses
The described procedures can be used to collect Total Suspended
Particulate (TSP) matter in ambient air. The collected material may be
extracted and analyzed for trace metals or particulate related organics of low
volatility. In the latter case, backup collection techniques (PUF) would be
advisable.
4-30
-------
FILTER
POSITION
RETAINING
RING
ADAPTER
FACE
PLATE
GASKET
GASKET
GROMMET
ADAPTER
JNTING
PLATE
MOUNTING\<\
: \
• ft GASKFT HOUSING PLATE
BRUSH-41 b£SKtT
11
MOTOR
x/^
Source: Reference 35.
- »VIRE
CORD
NUT a BOLT
ROTAMETER
CONDENSER
AND CLIP
Figure 19. Exploded view of typical high-volume air sampler parts.
Source: Reference 35,
Figure 20. Assembled sampler and shelter.
4-31
-------
Procedure for Use
1. Calibration
Refer to 40 CFR 50, Appendix B, Part 8.0—Calibration as
amended -1 and the EPA Proposed Changes to Ambient Measurement
Methodology for Carbon Monoxide, Particulates, Sulfur Dioxide, 47 FR
2341, January 15, 1982.37
Essentially, samplers must be calibrated when first purchased, after
major maintenance on the sampler (e.g., replacement of motor or
brushes), any time the flow measuring device (rotameter or recorder)
has been replaced or repaired, or any time a one-point calibration
check deviates from the calibration curve by more than j^6 percent
The following procedure is based on the use of a certified variable
resistance orifice as the sampler calibration device and a
continuous flow-rate recorder (Dickson recorder) used to ensure the
accuracy of air volume measurements. Samplers may also be equipped
with an electronic flow controlling mechanism to perform the same
function. Flow-rate controllers and recorders are not as yet
required; however, errors resulting from nonconstant flow rates can
be greatly reduced by using such devices. In addition, the
currently approved flow indicators (rotameters) have been shown to
be subject to a variety of errors caused by physical damage, dirt
deposition, and flow restrictions in connecting tubing.
a. Remove filter retaining plate from the sampler to be calibrated
and place a clean filter in the filter holder.
b. Attach the variable resistance orifice (VRO) to the sampler and
position the orifice setting to full open. Secure the VRO fall
plate to insure an air tight seal with the orifice gasket.
Attach a slack tube manometer to the sampler unit.
c. Plug sampler into 120-volt source, while checking manometer to
insure that the orifice pressure drop does not exceed the range
of the manometer. Let the sampler run for about 5 minutes.
d. Turn motor off and place a fresh chart on the unit. The chart
should include the following information: high-volume sampler
identification, date and time of calibration,and operator's
name. The chart should be labeled "Calibration Data."
e. Check the recorder for proper operation, and zero the pen if
necessary.
f. Determine five approximately equally spaced intermediate points
which provide pressure drops between the desired maximum and
minimum operating point and record the following data on the
calibration sheet:
4-32
-------
1. pressure drop from the manometer (in. t
2. flow rate indicated on Dickson recorder.
Repeat three points centralized in the vicinity of the normal
sampler flow rate to insure accuracy in the field.
(The Dickson Recorder should be tapped gently prior to reading,
to insure that the recorder pen is in its final position.)
Record the airflow rate from the VRO high-volume calibration
curve for each flow recorder reading.
ACCEPTABILITY = 100
(Qo-Qc)
Qc
within 5%
where: Qo=observed flow rate
Qc=flow rate from calibrated curve
h. If the air flow rate exceeds the acceptable limits, rerun
points for which percent deviation exceeds 5 percent until
acceptance limits are attained.
i. Correct the sample flow rate to standard conditions using the
following formula:
~ T T P~~
Ll *2
where: 0,2 = corrected flow rate (scfm)
Q-j^ = flow rate from chart
T2 = absolute temperature (298°K) most sensitive
ranges first.
2. Sample Collection
Total suspended particulate measurements are normally collected over
a 24-hour sampling period; however, this requirement may be altered
for hazardous waste sampling applications. Monitoring objectives
may require sampling at specific time intervals only (e.g., during
drum excavations), and high particulate loadings due to heavy
equipment traffic may also require shortened sampling periods.
Sampling time selection will therefore be site specific and
obviously dependent upon a number of unique factors.
a. Installation of Clean Filter
(1) Remove faceplate by loosening the four wing nuts and
rotating the bolts outward.
4-33
-------
(2) Obtain a clean, weighed filter and record the filter
number, high-volume sampler serial number, flowmeter
serial number, location, run date, and start time on the
data sheet.
(3) Carefully place the clean filter rough side up, on the
wire screen, and center the filter so that when the
faceplate is in position, the gasket will form a tight
seal on the outside edge of the filter.
(4) Replace faceplate, being careful not to move the filter,
and tighten the wing nuts evenly until the gasket forms an
airtight seal against the filter.
Operation Checks
(1) Allow sampler motor to warm up at least 5 minutes to reach
normal operating temperature.
(2) Assure that the flow recorder is connected to the sampler
using the same tubing as was used to calibrate the sampler.
(3) Place a new chart on the recorder and set at correct start
time.
(4) Record "Run Start" time and date, site identification, and
sampler number on the chart.
(5) Turn sampler off and set clock switch to desired setting.
Total suspended particulate samples are normally collected
over a 24-hour period; however, this requirement may be
altered depending on monitoring applications.
Removing Exposed Filter
(1) Turn sampler "on" and allow to warm up at least 5 minutes.
(2) Check flow recorder chart for proper operation.
(3) Turn sampler "off" and record elapsed time in logbook and
on the data sheet.
(4) Remove chart and place in envelope.
(5) Carefully loosen wing nuts and remove faceplate gasket.
(6) Remove the exposed filter by gently grasping the ends of
the filter and lifting it from the screen. Fold the
filter lengthwise at the middle with the exposed side
"in." If the collected sample is not centered on the
filter> fold the filter accordingly so that sample touches
sample only.
4-34
-------
(7) Place the filter in a glassine envelope, and place
glassine envelope with data sheet in a folder for return
to sample bank.
(8) Visually inspect for signs of leakage, damage, etc., to
the sampler and repair if necessary.
Sources
United States Environmental Protection Agency. "Appendix B—Reference
Method for the Determination of Suspended Particulates in the Atmosphere
(High Volume Method)". 40 CFR Part 50. November 25, 1971.
United States Environmental Protection Agency. "Proposed Changes to
Ambient Measurement Methodology for Carbon Monoxide, Particulates and
Sulfur Dioxide." 47 CFR 2341. January 15, 1982.
4-35
-------
SOIL GASES AND VAPORS
Monitoring of soil gases can often serve as a quick method of determining
the extent of pollutant migration or establishing perimeters of a site
containing buried wastes. Soil-gas exchange with the ambient atmosphere
greatly dilutes gaseous components making them difficult to detect.
Therefore, sampling in the soil can provide a more concentrated source for
underground waste detection. Soil-gas sampling also has particular
applicability to the identification of methane fluxes at sanitary landfills.
4-36
-------
METHOD IV-9: MONITORING GAS AND VAPORS FROM TEST HOLE
Discussion
Gas samples can be withdrawn from test holes by using a nonsparking
probe, brass and Teflon being the most suitable. The probe is then attached
to the gas inlet of the desired gas monitor such as those described in the
ambient gases section and Method IV-1 through IV-7. The test holes are easily
prepared by driving a metal rod (approximately 1 in. diameter) into the soil
with a drive weight. Commercial bar hole-makers are available that combine
O O
the steel hole-making bar and drive weight into one unit (see Figure 21). °
Uses
This system is particularly adapted for rapid evaluation of waste sites
for soil gas generation. When used in conjunction with a hydrocarbon analyzer
or an explosimeter it can rapidly determine the areal extent of a waste site
or the location of a particular emission source. It is recommended that the
test area be screened with a metal detector before sampling.
Procedures for Use
1. Select location free from rocks and debris. Screen location with
metal detector to varify absence of drums and pipes.
2. Place bar point on ground and raise drive weight, then allow weight
to fall on bar. It is only necessary to guide the weight in its
vertical travel.
3. Continue until desired depth or any penetration resistance is
reached.
4. Remove bar hole-maker.
5. Attach suitable length of Teflon tubing (stainless steel or brass
may be used in some instances but may result in some gas
adsorption/absorption) to monitor instrument gas inlet.
6. Lower tubing into test hole and operate monitor or gas sampling
device as listed in Methods IV-1 through IV-7.
7. Record results.
8. Remove sample tubing and observe that instrument readings return to
background. If not, change tubing before proceeding to next test
location.
9. Tramp over and recover test hole.
Sources
Flower, F.B. "Case History of Landfill Gas Movement Through Soils."
Rutgers University, New Brunswick, New Jersey.
4-37
-------
6cm
60cm
V
DRIVE WEIGHT
STEEL BAR (al.Zcm OD x 100cm)
Figure 21. Bar hole-maker.
4-38
-------
METHOD IV-10. MONITORING GAS AND VAPORS FROM WELLS
Discussion
The sampling of wells for gases and vapors can be accomplished by
lowering an intake probe through a sealed cap on the top of the well, (Figure
22). The intake probe should be of a nonsparking material that will further
minimize adsorption or desorption effects. Teflon or glass are preferable to
steel or brass in this application. The intake probe is then connected to the
desired gas monitor such as those described in the ambient gases section and
Methods IV-1 through IV-7.
Uses
Existing groundwater monitoring wells can be used to check for the
presence of those gases volatilized or otherwise liberated from the
groundwater. In some cases, the groundwater level will be below the top of
the screened portion of the well allowing free soil gases to enter the well
casing.
Wells especially designed for soil-gas monitoring can also be placed by
conventional well placement techniques. The well casing, however, is
perforated the entire distance the annular space is packed with gravel, and
the top is sealed with a grout cap.^9 The top of the casing can even be
equipped with a sampling valve to allow easy coupling to the monitoring
instruments.
Procedures for Use
1. Sound the well for water level or bottom.
2. Select the required length of Teflon tubing. It should be of
sufficient length to approach the water level or well bottom, but
not so long as to allow water or bottom sediments to enter probe
inlet. An inside diameter of 1/8 inch is usually sufficient.
However, because this size lacks rigidity, a small weight can be
secured to the inlet end to facilitate lowering.
3. Lower the tubing through an appropriate sized stopper on the top of
the well casing. A wooden plug serves well. It is not critical to
maintain an effective seal around the tubing.
4. Lower intake to near bottom and attach outlet to monitor inlet.
5. Proceed with instrument operation according to methods III-l through
III-7 or the instrument operator's manual. Note: When using an
adsorption technique for qualification/quantification Sisk^
recommends a sample rate of 1pm for 5 to 30 minutes through Tenax GC
(see Method IV-6).
4-39
-------
Y/fa
'•Xi
* « *,
» " * *
0 »
'** '
> t» *
.',"',
V
* » * ,
tf 0 »
* •
* t
* *
* *
» 0 .
• o o
e " •
V/i
^* .
^ * %
»'. •
* • *
, . *
• 0 *1
* • * *
• * i.
/
8
1
^
^
^
, — •
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S
3?
1
i
k—
-— /=-
^
<^
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!•'.,,
''•>
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i-V/
f * * *
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'» « »
r';';
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Sr—*
' '
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r. .
GAS SAMPLING VALVES
^-METAL CAP
^-CEMENT GROUT CAP
^GRAVEL PACKING
— GAS COLLECTION
PORT
Source: Reference 39.
Figure 22. Gas sampling well.
4-40
-------
6. Gradually raise the intake tubing while observing the instrument
readings.
7. Record readings, then remove probe and close casing.
8. If instrument fails to return to background readings, replace sample
inlet tube before proceeding to next well. Note: Sometimes vapors
may condense on the lower portion of the sample tube, merely cutting
off the bottom several centimeters of the intake tube will remove
the source of contamination and allow reuse of the remaining sample
tube.
Sources
Hatayama, H.R. "Special Sampling Techniques Used for Investigating
Uncontrolled Hazardous Waste Sites in California." In: National
Conference on Management of Uncontrolled Hazardous Waste Sites.
Hazardous Material Control Research Institute, Silver Springs, Maryland.
1981.
4-41
-------
HEADSPACE GASES
Headspace gases are the accumulated gaseous components found above solid
or liquid layers in closed vessels. These gases may be the result of
volatilization, degradation, or chemical reaction. Poorly ventilated or
partially sealed areas can also act to concentrate gas vapors. Component
concentrations normally exceed those found in ambient measurements.
Therefore, the previously described ambient methods must be modified for
handling these higher concentrations and for the remote sensing of container
contents. The anticipated higher concentrations can be dealt with by altering
the instrument detector range, reducing the sample gas flow rate into the
instrument, or utilizing a sample dilution system. These techniques are
necessary for the prevention of saturation, poisoning, and/or gross
deterioration of the detector element.
Most ambient measurement devices have sample intakes which are highly
directional and localized. The use of an extension will allow the operator to
obtain samples from varying depths and distances within containers while
maintaining a safe position.
Headspace gases are often found in certain types of containers. Bulging,
stainless steel, lined, or other special designated drums are more likely to
contain hazardous headspace gases. A preliminary scan of the external seams,
edges, or any corroded areas with a vapor analyzer may indicate the nature of
the contents.
Poorly ventilated vessels can usually be sampled for headspace gases
through small hatches or openings. Fully sealed vessels must be approached
more cautiously since breaching may result in the uncontrolled release of
pressurized gases or the potential for violent reactions with the ambient
atmosphere. Any decision to open a sealed vessel should be based on sound
need and the investigator must be cognizant of the inherent dangers.
4-42
-------
METHOD IV-11: SAMPLING OF HEADSPACE GASES IN SEMISEALED VESSELS
Discussion
Sampling of headspace gases involves merely extending the intake or
otherwise conducting the contained gas to the detection device. Any of the
procedures discussed in the ambient section (Methods IV-1 through IV-7) can be
employed. The use of Teflon tubing of approximately 4.8 or 6.4 mm (3/16 or
1/4 inch) inside diameter works well as a probe extension.
Uses
This system is viable in a wide variety of applications. It is simple,
and only requires some adaption to match the extension tubing to the
instrument intake. The likelihood of high concentrations of contaminants is,
however, greater in contained vessels and, as a result, there is the potential
for detector saturation and fouling. It is advisable to place any instruments
used in this role in their highest operating range. Flame ionization
detectors that utilize the sample gas stream as their combustion air may have
insufficient oxygen for combustion and will require use of a dilution probe.
The introduction of entrained droplets from the container contents should also
be avoided. Careful handling of the extension tube to avoid close contact
with the materials surface and in some instances the use of a glass wool
filter plug will prevent material buildup in the probe and detector.
Procedures for Use
1. Select an appropriate monitoring instrument or device that will
characterize the gas if present. A combustible gas detector,
hydrocarbon vapor analyzer or stain detector tube is normally used.
Be particularly aware of the limitations of the instrument in use.
2. Attach the proper size and length tubing that will reach into the
container. The tubing seal with the monitoring instrument should be
leak tight.
3. Insert tubing into container or vessel opening and operate
instrument as per Methods IV-1 through IV-7 and the appropriate
operators manual.
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METHOD IV-12: SAMPLING OF HEADSPACE GASES IN SEALED VESSELS
Discussion
Sealed vessels, especially 55-gallon drums, present problems when
sampling for entrapped gases. The container must be opened to accept a sample
probe while still preventing uncontrolled release of its potentially hazardous
contents. Further, this must be accomplished while still protecting the
safety of the inspector.
On large vessels and tanks inspection valves and petcocks are normally
available. Sealed drums, however, are not designed to contain gases that
often develop as reaction products of the contents and have no such provisions.
Leak-free sample tops can be installed on these drums by attaching a
mechanism that will drill through a leak-tight fitting strapped to the drum
(Figure 23). The system consists of a battery operated drill with a remote
control switch. The drill is mounted on a simple spring-controlled frame
which guides the drill bit through a Swagelok cross fitting. The Swagelok
cross is attached to a ball valve which, in turn, is attached to a mounting
plate. The mounting plate underside is gasketed with closed cell Neoprene
foam. The mounting plate is held against the container using standard steel
packaging straps. The cross fitting contains a Teflon seal which allows the
drill bit to rotate without allowing gases from the container to escape during
drum penetration. A pressure gauge is attached to one side of the Swagelok
cross while a needle valve is attached to the side opposite the gauge. The
pressure gauge permits the waste handler to observe the internal pressure of
the container while the valve permits the removal of sample gas for analysis.
The valve and pressure gauge can also be used to insure pressure equalization
prior to further opening of the container. A light is located on the remote
control switch which indicates when the drum has been pierced. The electrical
control system is interlocked so that drill operation automatically stops upon
penetration of the container by the drill bit. The whole assembly is
activated remotely. Once the bit has penetrated the drum, contained gases
flow between the drill bit and the inside of the fittings. Release of the
gases is controlled by a needle valve. After sampling, the drill mechanism is
pulled away from the container until the drill bit clears the ball valve. The
ball valve is then closed, and the piercing mechanism up to the ball valve is
removed from the container. The ball valve and mounting plate are left intact
to serve as a permanent seal for the opening.
The monitors and detectors described in the Ambient Section (Methods IV-1
through IV-7) can then be adapted to the needle valve and the gas directed to
the instrument.
Uses
This device has been used on 55-gallon drums but would also be applicable
to other size drums and vessels. Fabrication specifications for this device
are found in Appendix B.
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SPRING
LOADING
CUT-OFF
SWITCH
DEPTH STOP
BALL
VALVE
Source: Reference 40.
Figure 23. Drilling mechanism,
4-45
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Procedures for Use
1. Assemble the drill assembly as per Appendix B - Equipment
Availability and Fabrication.
2. Brush clear any loose rust or dirt to assure a leak-free seal. Seat
assembly against the drum side. Tighten mounting straps using
portable packaging equipment.
3. Assure that all fittings are snug and needle valve is fully closed.
4. Deploy remote control cable to full extent and stand behind safety
screen.
5. Activate drill.
6. After penetration is indicated by light on remote control unit,
approach container while monitoring internal drum pressure with
pressure gauge on sampler.
7. Attach desired monitor instrument for container content
characterization. Any device listed in the ambient section can be
employed (Method IV-1 through IV-7). The instrument can be attached
by using an appropriate size teflon tubing (see Method IV-11).
After sampling, close needle valve.
8. After proper quantification and/or identification of the contained
gas, the safety officer should decide whether the gas can be vented
or should be properly contained for later disposal.
9. The full assembly can be removed if the gas has been properly vented
or disposed of; otherwise the drill can be loosened from the bit and
removed from the guide assembly as outlined below.
a. Pull drilling mechanism away from container until the drill bit
clears the ball valve. Close ball valve.
b. Loosen nut containing Teflon seal.
c. Unscrew bolts, holding drill assembly to mounting plate.
d. Remove drill assembly from mounting plate pulling drill bit
through Teflon seal.
e. Remove cross fitting as unit from ball valve.
The remaining mounting plate and ball valve serve as a permanent
seal until the container can be disposed of properly.
4-46
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Sources
Snyder, Roger., Tonkin, Martha E., McKissick, Alton M., "Development of
Hazardous/Toxic Wastes Analytical Screening Procedures," Atlantic
Research Corporation, July 1980.
4-47
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SECTION 5
IONIZING RADIATION
GENERAL
Radiation monitoring should be one of the first tasks performed when
initially approaching a waste site or hazardous material spill. This
requirement is dictated by the potential risk to human health on contact with
a radioactive source as exposure to even small amounts of energy may result in
marked biological damage.
Radiation monitoring for hazardous waste situations essentially involves
two approaches; personnel monitoring and survey monitoring. Personnel
monitoring involves the use of instruments designed to measure total
cumulative radiation exposure in units that can be related to the absorbed
dose. The instruments used are worn or carried directly by the personnel
being monitored and consist of such devices as film badges, pocket dosimeters
and pocket chambers. Survey instruments are meant to measure ionizing
activity as it relates to the exposure rate (in units of milliroentgens/hr) or
disintegration rate (counts/minute). As do personnel monitors, these devices
rely on the ability of radiation to cause ionizations and consist of
ionization chambers, proportional counters, Geiger-Mueller instruments, and
scintillation devices. They are particularly useful in performing initial
field surveys to detect and locate the presence of radioactive sources and in
drum screening procedures performed prior to further drum handling (i.e.,
staging, sampling, compositing, etc.).
Although all of these detection instruments rely on the ability of
radiation to cause ionization, each differs in its sensitivity, i.e., its
ability to detect different types and varying intensities of radiation.
Basically there are four main groups of ionizing radiation types. These
include:
• heavy, positively charged particles such as alpha particles,
protons, deuterons, tritions, and possibly mesons each of which
exhibit similar mechanisms of interaction with matter;
• beta particles including both positrons and electrons;
• electromagnetic radiation including x-ray and gamma radiation; and
• neutrons.
5-1
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For the purposes of this section, however, only alpha, beta and gamma
radiation will be discussed, as they are the types most likely to be
encountered at a hazardous waste site.
Alpha particles are characterized as a charged particle having two
protons and two neutrons and, due to this large mass and charge (in addition
to high velocity), have a high probability of interacting or colliding with
orbital electrons and atomic nuclei. They have a limited tissue penetration
ability, however, since this type of radiation tends to lose its energy over
short distances. It is therefore easy to shield against and poses little
threat outside of the human body. However, due to its high specific
ionization, alpha radiation is capable of totally destroying cellular material
if it is able to locate within the body (e.g., by ingestion, inhalation, etc.).
Beta particles are negatively charged particles that can be construed as
high-speed electrons. In contrast with electrons, however, beta particles
orginate in the nucleus. They exhibit medium penetration and specific
ionization when compared to alpha particles, and, although they pose a greater
external body threat than alpha, particles of low energy are usually stopped
by the horny dead layers of the skin. Particles with enough energy to
penetrate the basal layer of the epidermis, however, still pose an external
threat. They can be shielded by a few millimeters of aluminum and, like alpha
particles, generally present a greater threat if located inside the body.
Gamma radiation is a type of electromagnetic radiation of nuclear origin
with a zero rest mass and no charge. It has the lowest specific ionization of
the three classifications and possesses the ability to penetrate tissue for
great distances. It therefore constitutes the greatest external radiation
hazard (in comparison to alpha and beta) as it is capable of deep penetration
within the body and is a threat to all organs. For this reason gamma
radiation is the most routinely monitored radiation type at hazardous waste
sites and environmental spills.
PERSONNEL MONITORS
Although no specific method is outlined in this manual for personnel
radiation monitors (this is best covered by individual manufacturer
instructions), it is important that their existence and basic characteristics
be mentioned in this section. For this reason, the three basic types of
personnel monitors, namely film badges, thermoluminescent dosimeters, and ion
chambers, will be discussed as to the specific characteristics and relative
advantages of each.
Film Badge
The use of films for monitoring personnel exposure is considered to be
the most practical, although least accurate, of the existing methods. The
method employs a gelatin base with a silver halide spread on film or glass.
Radiation interacts within the silver halide in the emulsion by means of
ionizations, thereby causing the formation of a latent image which, upon
development, is converted into a black deposit of metallic silver. This
5-2
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darkening can then be related to the type, energy, and quantity of radiation
received by the film badge. It is capable of recording a permanent record of
personnel exposure.
Thermoluminescent Dosimeters
Thermoluminescent dosimeters (TLD) can replace film badges for most
applications. In general they are more sensitive and more accurate than film
badges and can be processed more quickly and less expensively. These devices
detect radiation by storing ionization energy in defects of the crystal latice
of certain doped solids, such as LiF (Mn) and Ca F2 (Mn). The altered
energy levels are read out by heating the solid which then releases visible
light. The light output is proportional to the absorbed radiation energy and
can be related to exposure or dose units. TLD's can be reused but do not
provide a permanent record of exposure because the information is erased upon
readout. A permanent record is kept in the form of the original glow curve
(light output vs. time (or temperature)) trace which can be stored on paper or
in electronic memory.
Self-Reading Dosimeter
A self-reading dosimeter is essentially an ion chamber containing two
electrodes, one being a thin quartz loop free to move with respect to its
mounting and the other a fixed heavy quartz fiber. Like charges are placed on
both loops causing the movable one to be repelled from the fixed loop.
Ionization entering the chamber reduces the charge on the loops allowing the
movable one to return towards its neutral position, the distance being
proportional to the dose received in the chamber. The device also includes an
optical system and transparent scale which permits instant results at any time
without external readers. They are rugged, sensitive instruments small enough
to be worn comfortably and extremely useful for measuring integrated exposure
levels.
Pocket Chambers
A pocket ion chamber is basically a cylindrical electrode and a coaxial
collecting rod which is insulated from the rest of the device. A charge is
placed on the collecting rod, and this charge is subsequently reduced when
ions formed upon exposure to radiation collect on the rod. The main
disadvantage of the pocket chamber is that the collecting-rod charging
procedure and the determination of exposure must be accomplished externally on
a unit called a "charger-reader." The main advantages of pocket chambers, in
comparison to the direct-reading dosimeter, are the low cost and simplicity.
SURVEY INSTRUMENTS
Radiation survey instruments must meet the same criteria as previously
outlined for other monitors used at hazardous waste sites. They should be
portable, rugged, sensitive, simple in design and operation, reliable, and
intrinsically safe for use in explosive atmospheres. No one survey instrument
5-3
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or type of instrument can be expected to totally meet all of these criteria
and the investigator must be aware of the characteristics
(and limitations) of each type of detector.
Of primary concern is instrument sensitivity as there are a number of
field instrument types that are unique to the type and level of radiation they
will respond to. This discussion will be limited to ionization chambers,
proportional counters, Geiger-Mueller counters, and scintillation detectors.
Ionization Chambers
Ionization chambers are instruments in which the ionization initially
produced within the chamber by radiation is measured without further gas
amplification. It consists of a gas-filled envelope (usually air at
atmospheric pressure) with two electrodes at different electrical potentials.
The walls of the tube generally serve as the cathode and a wire mounted down
the center of the tube serves as the anode. Ionizing radiation entering the
chamber produces ions which migrate towards the electrode due to the applied
potential, producing a current. This current requires amplification to a
measurable level before it can be recorded on a meter. These are high-range
instruments (low sensitivity) and are used extensively for measuring high
intensity beta, gamma, or x-radiation. No aural indication is possible with
these instruments and operators must be constantly aware of the meter to
determine radiation intensity. Ionization chambers do not record individual
radiation particles but integrate all signals produced as an electric current
to drive the meter. They should be calibrated to the type and intensity of
radiation desired to be measured and are capable of reading in
milliroentgens/hr (or roentgens/hr) or counts/minute.
Proportional Counter
Instruments of this type derive their name due to their operation in the
proportional region of the typical instrument response curve. Instrument
probes have an extremely thin window that allows alpha particles to enter and
as such are used extensively for this purpose by adjusting instrument
operating parameters to discriminate against beta and gamma radiation. The
meter is read in counts per minute and usually has several sensitivity
scales. It should be noted that due to the nature of alpha particles, it is
important to hold the probe as close as possible to (though not in contact
with) the surface being monitored. The proportional counter is generally more
delicate in construction than the other listed devices and therefore may not
be considered appropriate as a field instrument.
Geiger~Mueller Counter
These instruments operate principally in the same manner as ionization
chambers except that secondary electrons are formed allowing for greater
sensitivity. The chambers are filled with an inert gas such as argon, helium,
or neon (below atmospheric pressure) and a quenching gas which functions to
control the secondary electron formation. These instruments are very
sensitive and are commonly used to detect low level gamma and/or beta
radiation. Meters are read in counts/minute or milliroentgens/hour. The
5-4
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amplification process inherent in this type of detector allows a single beta
particle or gamma photon to be detected. It should be noted that these
devices are sensitive instruments and care should be taken not to exceed their
maximum capacity to prevent damage to the GM tube.
Scintillation Detectors
These devices depend upon light produced when ionizing radiation
interacts with a media (solid crystal used in survey instruments). The
produced flashes of light or scintillations fall onto a photomultiplier tube
which converts them to electrical impulses. These impulses are amplified and
subsequently measured to give an indication of the level of radiation
present. These are extremely sensitive instruments used to detect alpha,
beta, or gamma radiation simply by choosing the correct crystal. Alpha
particles are detected with a silver activated zinc sulfide screen, beta
radiation with an anthracene crystal (covered with a thin metal foil to screen
alpha particles), and gamma or x-ray with a sodium iodide crystal. The
instrument can be calibrated in the same manner as in ion chambers and Geiger-
Mueller instruments. The operator should keep in mind that in older models
the photomultiplier tube may be damaged if directly exposed to light without
first disconnecting the voltage.
5-5
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METHOD V-l: RADIATION SURVEY INSTRUMENTS
Discussion
As previously noted, a variety of radiation survey instrumentation
exists, each capable of responding to different types and levels of ionizing
radiation. The procedure delineated below is therefore purposely general and
simply outlines common instrument features and operational steps. It is by no
means meant to replace the instrument instruction manual but is only meant to
serve as a supplemental guide.
Uses
Radiation survey instruments are used to detect the presence of
radioactive sources and are useful in assisting personnel in the making of
decisions concerning personal safety requirements, levels of contamination
present, and transportation and disposal considerations.
Procedures for Use
1. Choose an instrument or interchangeable detector tube which is
consistent with the investigative requirements.
2. Turn selector switch to the standby or the warm-up position and
allow instrument to warm-up for 1-2 minutes.
3. Turn instrument selector switch to battery check position and check
battery strength.
4. Turn range selector switch to desired level or scale factor (e.g.,
100X, 10X, IX, 0.1X for counts/minute scale) and check or calibrate
instrument with a radioactive check source (if available).
5. Turn audio switch on if desired.
6. Choose needle response (fast/slow response).
7. Turn range selector to most sensitive setting and determine natural
background radiation (0.01-0.02 mR/hr).
8. Choose a survey range and scan suspected surfaces or areas. When in
doubt, use most sensitive ranges first. Read scale in mR/hr or
counts/minute.
Sources
Department of Health and Human Services, Bureau of Radiological Health,
Radiological Health Handbook. USGPO (017-011-0004309).
U.S. Environmental Protection Agency. "Hazardous Materials Incident
Response Operations Training Manual." National Training and Operational
Technology Center, Cincinnati, Ohio.
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SECTION 6
REFERENCES
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SECTION 7
BIBLIOGRAPHY
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Josephson, J. Safeguards for Groundwaters. Environmental Science and
Technology, l4(l):38-44, 1980.
Lentzen, D. E., D. Wagoner, E. D. Estes, and W. F. Gutknecht. IERL-RTP
Procedures Manual: Level 1 Environmental Assessment (second ed.).,
EPA-600/7-78-201, 1978.
MacLeod, K. E. and R. G. Lewis. Measurement of Contamination from PCB Sources
In: Sampling and Analysis of Toxic Organics in the Atmosphere, ASTM STP
721, Philadelphia, PA, 1980.
MacLeod, K. E. Polychlorinated Biphenyls in Indoor Air. Environmental Science
and Technology, 7(11), 1981.
Maddalone, R. F. Technical Manual for Inorganic Sampling and Analysis.
EPA-600/277-024, 1977.
Mason, Benjamin, J. Protocol for Soil Sampling: Techniques and Strategies.
Contract No. CR 808529-01-2, U.S. Environmental Protection Agency,
EMSL-LV, March 30, 1982.
Milletari, A. F. Sampling Industrial Wastewater to Help Meet Discharge
Standards. Water and Wastes Engineering, 14(10):55-57, 1977.
7-2
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Monsanto Corp. Technical Manual for Process Sampling Strategies for Organic
Materials. EPA-2-76-122, IERL, 1976.
Peters, J. A., K. M. Tackett, and E. C. Eimutis. Measurement of Fugitive
Hydrocarbon Emissions from a Chemical Waste Disposal Site. In: National
Conference on Management of Uncontrolled Hazardous Waste Sites,
Washington, D.C., 1981.
Pellezzari, E. D. Development of Method for Carcinogenic Vapor Analysis in
Ambient Atmospheres. EPA 650/2-74-121, 1974.
Pettyjohn, W. A., W. J. Dunlop, R. Crosby, and W. J. Keely. Sampling
Groundwater for Organic Contaminants. Groundwater. 19(2), 1981.
Pickens, J. F., J. A. Cherry, G. E. Grisak, W. R. Merrit and B. A. Risto.
A Multilevel Device for Groundwater Sampling and Piezometric Monitoring.
Groundwater, 15(5), 1977.
Rhodes, J. W. and D. E. Johnson. Evaluation of Collection Media for Low Levels
of Airborne Pesticides. EPA 600/1-77-050, 1980.
Robertson, J. Organic Compounds Entering Ground Water from a Landfill.
National Environmental Research Center. PB-237-969, 1974.
Schofield, T. Sampling Water and Wastewater. Practical Aspects of Sample
Collection. Water Pollution Control, 79:468-470, 1980.
Sullivan, D. A. and J. B. Strauss. Air Monitoring of a Hazardous Waste
Site. In: National Conference on Management of Uncontrolled Hazardous
Waste Sites, Washington, D.C., 1981.
Williams, R. B. A Sample Substrate Core Sampler. Lab. Pract., 29(6):637,
1980.
7-3
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APPENDIX A
SAMPLE CONTAINERIZATION AND PRESERVATION
A-l
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Acidity and Alkalinity
Apparatus and Materials:
• Polyethylene or borosilicate glass (Pyrex or equivalent) bottles.
Sample Collection, Preservation, and Handling:
• Fill sample bottles completely and cap tightly.
• Store samples at 4°C.
• All samples should be analyzed within 14 days of collection.
Quality Control:
• Dissolved gases contributing to acidity or alkalinity, such as
carbon dioxide, hydrogen sulfide, or ammonia, may be lost or gained
during sampling or storage. Sample bottles must be capped and
sealed tightly, avoiding sample agitation or prolonged exposure to
air.
A-2
-------
Asbestos
Apparatus and Materials:
• 1-liter Polyethylene bottles
Sample Collection, Preservation and Handling:
• Leave air space at the top of the sample container to allow for
shaking the sample.
• Avoid contacting the sample with acid
• If the sample cannot be filtered within 48 hours of collection, add
1 ml of a 2.71 percent solution of mercuric chloride per liter of
sample to prevent bacterial growth.
• Store at 4°C
Quality Control:
• The sample bottle should be rinsed at least twice with the water
that is being sampled.
A-3
-------
Bacteria
Apparatus and Materials:
Polypropylene or glass bottles. Samples for bacteriological
examination must be collected in bottles that have been cleansed and
rinsed with great care, given a final rinse with distilled water,
and sterilized.
Bottles of glass capable of being sterilized and of any suitable
size and shape may be used for samples intended for bacteriologic
examination. Bottles shall hold a sufficient volume of sample for
all the required tests, permit proper washing, and maintain the
samples uncontaminated until the examinations are completed. Ground
glass stoppered bottles, preferably wide-mouth and of
break-resistant glass, are recommended. Polypropylene bottles of
suitable size, wide-mouth, and capable of being sterilized are also
satisfactory.
Metal or plastic screw cap closures may be used on sample bottles
provided that no volatile compounds are produced on sterilization,
and that they are equipped with liners that do not produce toxic or
bacteriostatic compounds on sterilization.
Before sterilization, cover the tops and necks of sample bottles
having glass closures with metal foil, rubberized cloth, heavy
impermeable paper, or milk bottle cover caps.
Glassware shall be sterilized for not less than 60 minutes at a
temperature of 170°C.
For plastic bottles that distort on autoclaving, low temperature
ethylene oxide gas sterilization should be used.
Sodium thiosulfate (ACS), 10 percent solution. When sampling water
contains residual chlorine, sodium thiosulfate should be added to
the clean sample bottle before sterilization in an amount sufficient
to provide an approximate concentration of 100 mg/1 in the sample.
This can be accomplished by adding to a 500 ml bottle, 0.4 ml of a
10 percent solution of sodium thiosulfate (this will neutralize a
sample containing about 15 mg/1 of residual chlorine). The bottle
is then stoppered, capped, and sterilized.
Water samples high in copper or zinc and wastewater samples high in
heavy metals should be collected in sample bottles containing a
chelating agent that will reduce metal toxicity. This is
particularly significant when such samples are in transit for 24
hours or more. Ethylenediaminetetraacetic acid (EDTA) is a
satisfactory chelating agent. A concentration of 372 mg/1 should be
A-4
-------
added separately to the sample bottle before sterilization (0.3 ml
of a 15 percent solution in a 500 ml bottle) or it may be combined
with the sodium thiosulfate solution before addition.
Sample Collection, Preservation, and Handling:
• When the sample is collected, leave ample air space in the bottle
(at least 2.5 cm or 1 in.) to facilitate mixing of the sample by
shaking, preparatory to examination. Care must be exercised to take
samples that will be representative of the water being tested and to
avoid contamination of the sample at the time of collection or in
the period before examination.
The sampling bottle shall be kept unopened until the moment it is to
be filled. Remove the stopper and hood or cap as a unit, taking
care to avoid soiling. During sampling, do not handle the stopper
or cap and neck of the bottle and protect them from contamination.
Hold the bottle near the base, fill it without rinsing, replace the
stopper or cap immediately, and secure the hood around the neck of
the bottle.
• Store samples at 4°C.
• All samples should be analyzed within 6 hours of collection.
Quality Control:
• The bacteriological examination of a water sample should be started
promptly after collection to avoid unpredictable changes. The time
and temperature of storage of all samples should be recorded and
should be considered in the interpretation of data.
A-5
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Bicarbonate/Carbonate
Apparatus and Materials:
• Polyethylene or glass bottles
Sample Collection, Preservation and Handling:
• Bicarbonate/Carbonate analysis should be performed onsite. If
onsite determination is not possible, completely fill the sample
bottle, leaving no headspace, and return it to the laboratory as
quickly as possible for analysis.
• Store sample at 4°C until analyzed.
Quality Control:
• Carbon dioxide may be lost or gained during sampling and storage.
Sample bottles must be capped and sealed tightly, avoiding sample
agitation or prolonged exposure to air.
A-6
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Biochemical Oxygen Demand (BOD)
Apparatus and Materials:
• Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
• If possible, avoid samples containing residual chlorine by sampling
before chlorination. Notify laboratory if sample is from a
chlorinated effluent.
• Store sample at 4° until analyzed.
• All samples should be analyzed within 48 hours of collection.
Quality Control:
• Samples for BOD analysis may undergo significant degradation during
storage between collection and analysis, resulting in a low BOD
value. Minimize reduction of BOD by promptly analyzing the sample.
A-7
-------
Bromide
Apparatus and Materials:
• Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
• There are no required preservation techniques, although storage at
4°C is recommended.
• All samples must be analyzed within 28 days of collection.
Quality Control:
• No special precautions.
A-8
-------
Carbonate
See Bicarbonate/Carbonate
A-9
-------
Chloride
Apparatus and Materials:
• Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
• No preservative necessary.
4 All samples must be analyzed within 28 days of collection.
Quality Control:
• No special precautions.
A-10
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Chlorine Demand
Apparatus and Materials:
• Polyethylene or glass bottles.
• Testing apparatus and reagents, if analysis is to be performed
onsite.
Sample Collection, Preservation, and Handling:
• Chlorine in aqueous solution is unstable, and the chlorine content
of samples or solutions, particularly weak solutions, will decrease
rapidly. Exposure to sunlight or other strong light or agitation
will accelerate the reduction of chlorine. Therefore, sample must
be analyzed onsite or brought immediately to the laboratory. The
maximum holding time is 2 hours.
Quality Control:
• Chlorine determinations must begin immediately after sampling.
Excessive light and agitation should be avoided.
A-ll
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Chromium VI
Apparatus and Materials:
• Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
• Store samples at 4°C.
• All samples must be analyzed within 24 hours of collection.
• Do not contact sample with acid
Quality Control:
• Serious errors may be introduced during sampling and storage by
failure to remove residues of previous samples from the sample
container; therefore, all containers and sampling equipment should
be thoroughly cleaned before use.
A-12
-------
Chemical Oxygen Demand (COD)
Apparatus and Materials:
• Polyethylene or glass bottles.
• Cone, sulfuric acid, H2S04 (ACS).
Sample Collection, Preservation, and Handling:
• Preserve the sample by acidification with cone, sulfuric acid to a
pH less than 2.
• Store samples at 4°C.
• All samples must be analyzed within 28 days of collection.
Quality Control:
• Unstable samples should be tested without delay.
A-13
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Color
Apparatus and Materials:
• Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
• Store samples at 4°C.
• All samples must be analyzed within 48 hours of collection.
Quality Control:
• No special precautions.
A-14
-------
Conductance
Apparatus and Materials:
• Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
• Store samples at 4°C.
• All samples must be analyzed within 28 days.
Quality Control:
• No special precautions.
A-15
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Cyanide, Total and Amenable to Chlorination
Apparatus and Materials:
• Polyethylene or glass bottles.
• Sodium hydroxide solution (ACS).
• Ascorbic acid.
Sample Collection, Preservation, and Handling:
• Because most cyanides are highly reactive and unstable, analyze
samples as soon as possible. Preserve the sample by addition of
2 ml of 10 N NaOH to raise the pH of the sample to 12 or above and
store in a closed, dark bottle at 4°C.
• If residual chlorine is present in the sample, add 0.6 g ascorbic
acid.
• All samples should be analyzed within 14 days of collection.
Quality Control:
• Maximum holding time is 24 hours when sulfide is present.
Optionally, all samples may be tested with lead acetate paper before
the pH adjustment in order to determine if sulfide is present. If
sulfide is present, it can be removed by the addition of cadmium
nitrate powder until a negative spot test is obtained. The sample
is filtered and then NaOH is added to pH 12.
A-16
-------
Fluoride
Apparatus and Materials:
• Polyethylene bottles.
Sample Collection, Preservation, and Handling:
• Polyethylene bottles are required for collecting and storing samples
for fluoride analysis. Always rinse the bottle with a portion of
the sample.
• All samples must be analyzed within 28 days of collection.
Quality Control:
• No special precautions.
A-17
-------
Hardness
Apparatus and Materials:
• Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
• Acidify with HN03 to pH <2, store samples at 4°C.
• Samples should be analyzed within 6 months of collection.
Quality Control:
• Serious errors may be introduced during sampling and storage by
failure to remove residues of previous samples from the sample
container; therefore all containers and sampling equipment should be
thoroughly cleaned before use.
A-18
-------
Hydrazine
Apparatus and Materials:
• Polyethylene or glass bottles.
Sample Collection, Preservation, and Storage:
• If the sample cannot be analyzed immediately, collect it under
acid. Add 90 ml of sample to 100 ml of (1 + 9) HC1.
Quality Control:
• Avoid contacting the sample with oxidizing agents which may diminish
the hydrazine content.
A-19
-------
Iodide
Apparatus and Materials:
• Polyethylene or glass containers.
Sample Collection, Preservation, and Handling:
• Store samples at 4°C, analyze within 24 hours of collection.
Quality Control:
• No special precautions.
A-20
-------
Iodine
Apparatus and Materials:
• Polyethylene or glass containers
Sample Collection, Preservation, and Handling:
• The samples must be analyzed onsite or brought immediately to the
laboratory. The maximum holding time is 2 hours.
Quality Control:
• Iodine determinations must begin immediately after sampling.
A-21
-------
Metals - Except Chromium VI
Apparatus and Materials:
• Polyethylene or glass bottles.
• Nitric acid (1 + 1): Mix equal volumes of cone, nitric acid, HNC>3
(ACS), with deionized water.
• Deionized water.
Sample Collection, Preservation, and Handling:
• Wash and rinse sample container thoroughly with 1+1 nitric acid,
then with deionized water before use.
• Acidify the sample with 1+1 nitric acid to a pH of 2.0 or less.
Normally, 3 ml of 1 + 1 nitric acid per liter should be sufficient
to preserve the samples. This will keep the metals in solution and
minimize their adsorption on the container wall.
• All samples should be analyzed within 6 months of collection. An
exception is mercury analysis, which must be completed within 28
days.
Quality Control:
• Serious errors may be introduced during sampling and storage by
failure to remove residues of previous samples from the sample
container; therefore, follow the described rinsing procedure for all
containers and sampling equipment.
A-22
-------
Nitrogen
Ammonia
Nitrate-Nitrite
Kjeldahl Nitrogen
A-23
-------
Ammonia
Apparatus and Materials:
• Polyethylene or glass bottles.
• Cone, sulfuric acid, H2S04 (ACS).
Sample Collection, Preservation, and Handling:
• In the event that a prompt analysis is impossible, add cone.
sulfuric acid to lower sample pH to less than 2.
• All samples should be analyzed within 28 days of collection.
• Store samples at 4°C.
Quality Control:
• The most reliable results are obtained from fresh samples*
A-24
-------
Kjeldahl Nitrogen
Apparatus and Materials:
• Polyethylene or glass bottles.
• Cone, sulfuric acid (H2S04) (ACS).
Sample Collection, Preservation, and Handling:
• Acidify samples with cone, sulfuric acid to a pH of 2.0 or less.
• Store samples at 4°C.
• All samples should be analyzed within 28 days of collection.
Quality Control:
• The most reliable results are obtained in fresh samples. If prompt
analysis is impossible, retard biological activity with the above
preservation method.
A-25
-------
Nitrate aad Nitrite
Apparatus and Materials:
• Polyethylene or glass bottles.
• Cone, sulfuric acid, ^$04 (ACS)
Sample Collection, Preservation, and Handling:
• Store samples at 4°C.
• All samples should be analyzed within 48 hours of collection.
• If nitrate or nitrate plus nitrite are to be determined, preserve
the sample by addition of t^SO^ to a pH of 2.0 or less.
Sulfuric acid should not be added to samples requiring analysis for
nitrite only.
Quality Control:
Nitrate and nitrite determinations should be made promptly after
sampling.
A-26
-------
Oil and Grease
Apparatus and Materials:
• Glass bottles.
• Cone, sulfuric acid (H2S04) (ACS).
Sample Collection, Preservation, and Handling:
• Collect a representative sample in a wide-mouth glass bottle and
acidify in the sample bottle with cone, sulfuric acid to a pH of 2.0
or less. If other parameters are to be analyzed for, collect a
separate sample for the oil and grease determination to avoid
subdividing the sample in the laboratory.
• Store samples at 4°C.
• All samples should be analyzed within 28 days of collection.
Quality Control:
• Great care should be exercised when collecting samples to ensure
that a representative sample is obtained. When information is
required about the average grease concentration of a waste over an
extended period, examine at individual time intervals to eliminate
losses of grease on sampling equipment during collection of a
composite sample.
A-27
-------
Organic s
Purgeables - Method 624
Extractables - Method 625
Pesticides/PCBs - Method 608
A-28
-------
Method 624 Purgeables
Apparatus and Materials:
The water sample is to be collected in two (2) 40 ml vials with
Teflon-faced silicone septa and screw caps and maintained at 4°C
until the sampler's responsibility has been relieved at the Sample
Bank.
Container Preparation
1. Wash 40 ml vials with screw caps (Pierce No. 13075 or
equivalent) and Teflon-faced silicone septa (Pierce No. 12722
or equivalent) separately, utilizing a solution of Alconox
detergent or equivalent, and hot tapwater.
2. Rinse thoroughly with deionized water.
3. Place vials, caps, and septa on precleaned aluminum foil (as
described above) in an oven and bake for one (1) hour at 105°C.
4. Allow the vials to cool with the septa properly inserted and
the caps screwed on loosely. Tighten down caps when cool.
5. Store vials in an area not subject to contamination by air or
other sources.
Sample Collection, Preservation, and Handling
• If the sample contains residual chlorine, add sodium thiosulfate as
a preservative (10 mg/40 ml is sufficient for up to 5 ppm Cl£) to
the empty sample bottles just prior to shipping to the sampling site.
• if aromatic compounds such as benzene, toluene and ethylbenzene are
to be determined one of the following procedures should be used to
minimize degradation of these compounds by microbial action.
- Collect about 500 ml of sample in a clean container. Adjust
the pH of the sample to about 2 by addition of 1+1 HC1. Cap the
container and invert once to mix; check the pH with narrow
range (1.4 to 2.8) pH paper. Transfer the sample to a 40 ml
vial as described below. If residual chlorine is present, add
sodium thiosulfate to another sample container and fill as
described below.
Alternatively, the addition of the HgCl2 to the sampling vial
(approximately 12 rag per 40 ml vial) has been found effective
for inhibiting microbial action.
A-29
-------
The following procedures apply to sampling directly with the sample
vial.
1. Collect a single undisturbed sample of water for the analysis
of volatile organics. Submerge the sample vial just below the
surface upside down and slowly invert. Accomplish this task
creating as little disturbance as possible.
2. Allow the vial to fill and reach equilibrium with its
surrounding reservoir for several seconds.
3. Place the cap over the mouth of the vial so that the septum is
properly oriented and screw down the cap firmly.
4. Invert the vial to discover any entrapped air bubbles. If such
is the case, the sample will be discarded and another 40 ml
vial selected and filled.
5. Collect a replicate sample per instructions above.
- Label the sample vials with the appropriate designated
sample tag.
- Place the properly labeled sample vials in an appropriate
carrying container maintained at 4°C throughout the
sampling and transportation period.
Analyze samples within 14 days.
Quality Control:
Standard quality assurance practices should be used with this
method. Field replicates should be collected to validate the
precision of the sampling technique.
Samples can be contaminated by diffusion of volatile organics
(particularly methylene chloride) through the septum seal into the
sample during shipment and storage. A field blank* prepared from
organic-free water and carried through the sampling and handling
protocol can serve as a check on such contamination.
*Field Blank. The field blank is defined as an appropriate volume of
"organic-free" water which has been sent to the sampling site and back to
the analytical laboratory in a container and bottle identical to the type
used to collect the samples. Field blanks and samples must be shipped in
separate containers. Wheft received in the lab, the field blank is dosed,
extracted ^vfttfcgfice.ntrated as if it were an actual sample.
and
-------
Method 625 Extractables (Base/Neutrals, Acids, and Pesticides)
Apparatus and Materials:
• Sampling equipment, for discrete or composite sampling.
Grab sample bottle - Amber glass, 1 liter to 1 gallon volume.
French or Boston Round design is recommended. The container must be
washed and solvent rinsed before use to minimize interferences.
Bottle caps - Threaded to fit sample bottles. Caps must be lined
with Teflon. Aluminum foil may be substituted if sample is not
corrosive.
Compositing equipment - Automatic or manual compositing system.
Must incorporate glass sample containers for the collection of a
minimum of 1000 ml. Sample containers must be kept refrigerated
during sampling. No plastic or rubber tubing other than Teflon may
be used in the system.
Sample Collection, Preservation, and Handling:
• Grab samples must be collected in glass containers. Conventional
sampling practices should be followed, except that the bottle must
not be prerinsed with sample before collection. Composite samples
should be collected in refrigerated glass containers. Automatic
sampling equipment must be free of Tygon and other potential sources
of contamination.
• The sample must be iced or refrigerated from the time of collection
until extraction.
• All samples must be extracted within 7 days and completely analyzed
within 30 days of collection.
Quality Control:
• Standard quality assurance practices should be used with this
method.
A-31
-------
Glassware must be scrupulously clean. Clean all glassware as soon
as possible after use by rinsing with the last solvent used. This
should be followed by detergent washing in hot water. Rinse with
tap water, distilled water, acetone and finally pesticide quality
hexane. Heavily contaminated glassware may require treatment in a
muffle furnace at 400°C for 15 to 30 minutes. Some high boiling
materials, such as PCB's, may not be eliminated by this treatment.
Glassware should be sealed/stored in a clean environment immediately
after drying or cooling to prevent any accumulation of dust or other
contaminants. Store inverted or capped with aluminum foil.
A-32
-------
Method 608 Organochlorine Pesticides and PCBs
Apparatus and Materials:
• Sampling equipment, for discrete or composite sampling.
Grab sample bottle - Amber glass, 1 liter or 1 quart volume. French
or Boston Round design is recommended. The container must be washed
and solvent rinsed before use to minimize interferences.
Bottle caps - Threaded to screw on to the sample bottles. Caps must
be lined with Teflon. Foil may be substituted if sample is not
corrosive.
Compositing equipment - Automatic or manual compositing system.
Must incorporate glass sample containers for the collection of a
minimum of 250 ml. Sample containers must be kept refrigerated
during sampling. No Tygon or rubber tubing may be used in the
system.
Sample Collection, Preservation, and Handling:
• Grab samples must be collected in glass containers. Conventional
sampling practices should be followed, except that the bottle must
not be prewashed with sample before collection. Composite samples
should be collected in refrigerated glass containers. Automatic
sampling equipment must be free of Tygon and other potential sources
of contamination.
• The samples must be iced or refrigerated from the time of collection
until extraction.
• All samples must be extracted within 7 days and completely analyzed
within 30 days of collection.
Quality Control:
• Standard quality assurance practices should be used with this method.
A-33
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Hydrogen Ion (pH)
Apparatus and Materials:
• Polyethylene or glass bottles.
• Electronic pH meter with temperature compensation adjustment. Glass
electrode: Glass electrodes are available for measurement over the
entire pH range within minimum sodium ion error types for high
pH-high sodium samples. Reference electrode: Use of calomel,
silver-silver chlroide, or other constant-potential electrode.
• Standard buffer solutions of known pH.
Sample Collection, Preservation, and Handling:
• The electrometric measurement of pH is the only method approved by
EPA. The determination should be made onsite. The maximum holding
time for any sample is 2 hours.
• Because of the difference between the many makes and models of
commercially available pH meters, it is impossible to provide
detailed instructions for the proper operation of every instrument.
In each case, follow the manufacturer's instructions. Thoroughly
wet the glass and reference electrodes by immersing the tips in
water overnight or in accordance with instructions. Thereafter,
when the meter is not in use for pH measurement, keep the tips of
the electrodes immersed in water.
Before use, remove the electrodes from the water and rinse with
distilled or demineralized water. Dry the electrodes by gently
blotting with a soft tissue. Standardize the instrument with the
electrodes immersed in a buffer solution with a pH approaching that
of the sample and note the temperature of the buffer and the pH at
the measured temperature. Remove the electrodes from the buffer,
rinse thoroughly, and blot dry. Immerse in a second buffer
approximately 3 pH units different from the first and note the
temperature of the buffer and the pH at the measured temperature;
the reading should be within 0.1 unit of the pH for the second
buffer. Rinse electrodes thoroughly, blot dry, and immerse in the
sample. Agitate the sample sufficiently to provide homogeneity and
keep solids in suspension. If the sample temperature is different
from that of the buffers, let the electrodes equilibrate with the
sample. Measure the sample temperature and set the temperature
compensator on the pH meter to the measured temperature. Note and
record the pH and temperature. Rinse electrodes and immerse in
water until the next measurement.
A-34
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When only occasional pH measurements are made, standardize the
instrument before each measurement. Where frequent measurements
are made, less frequent standardization (every 1 or 2 hours) is
satisfactory. However, if sample pH values vary widely, standardize
more frequently with a buffer having a pH within 1 to 2 pH units of
that sample. Measure with two or more buffers of different pH at
least once daily and more frequently if samples contain abrasive
solids or dissolved fluorides, in order to check the linearity of
response. When electrode response to two buffers 3 pH units apart
show differences greater than 0.1 pH unit, replace the glass
electrode.
Measurements of pH in high purity waters, such as condensate or
demineralizer effluents, are subject to atmospheric contamination
and require special procedures for accurate pH measurement.
Quality Control:
The glass electrode is relatively free from interference from color,
turbidity, colloidal matter, oxidants, reductants, or high salinity,
except for a sodium error at high pH. This error at a pH above 10
may be reduced by using "low sodium error" electrodes. When using
ordinary glass electrodes, make approximate corrections for the
sodium error in accordance with information supplied by the
manufacturer. Temperature exerts two significant effects on pH
measurement. The pH potential, i.e., the change in potential per pH
unit, varies with temperature, and ionization in the sample also
varies. The first effect can be overcome by a temperature
compensation adjustment provided on the better commercial
instruments. The second effect is inherent in the sample and is
taken into consideration by recording both the temperature and pH of
each sample.
A-35
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Phenols
Apparatus and Materials:
• Glass bottles.
• Concentrated Sulfuric Acid, H2SC>4 (ACS).
Sample Collection, Preservation, and Handling:
• Acidify sample with concentrated H2SC>4 acid to a pH of 2.0 or
less.
• Oxidizing agents, such as chlorine, should be removed immediately
after sampling by the addition of an excess of ferrous ammonium
sulfate.
• Store samples at 4°C.
• All samples should be analyzed within 28 days of collection.
Quality Control:
• Phenols in concentrations usually encountered in wastewaters are
subject to biological and chemical oxidation. It is recommended
that preserved and stored samples be analyzed as soon as possible.
A-36
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Orthophosphate
Apparatus and Materials:
• Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
• Store samples at 4°C.
• All samples must be analyzed within 48 hours of collection.
Quality Control:
* Do not store samples containing low concentrations of phosphorus in
plastic bottles because phosphate may be adsorbed onto the walls of
the bottles. Rinse all glass containers with hot dilute HC1, then
rinse several times in distilled water. Never use commercial
detergents containing phosphate for cleansing glassware used in
phosphate analyses.
A-37
-------
Phosphorus, Total
Apparatus and Materials:
• Polyethylene or glass bottles.
• Cone, sulfuric acid (l^SC^) (ACS).
Sample Collection, Preservation, and Handling:
• Acidify sample with cone, sulfuric acid to a pH of 2.0 or less.
• Store samples at 4°C.
• All samples must be analyzed within 28 days of collection.
Quality Control:
• Do not store samples containing low concentrations of phosphorus in
plastic bottles because phosphate may be adsorbed onto the walls of
the bottles. Rinse all glass containers with hot dilute HC1, then
rinse several times in distilled water. Never use commercial
detergents containing phosphate for cleansing glassware used in
phosphate analyses.
A-38
-------
Radioactivity
Apparatus and Materials:
• Polyethylene or glass bottles.
• Cone, nitric acid (HN03) (ACS).
Sample Collection, Preservation, and Handling:
• Acidify samples with cone, nitric acid to a pH of 2.0 or less.
• All samples must be analyzed within 6 months of collection.
Quality Control:
• The principles of representative sampling of water and wastewater
apply to sampling for radioactivity examinations. When radioactive
industrial wastes or comparable materials are sampled, consideration
should be given to the deposition of radioactivity on the walls and
surfaces of glassware, plastic containers, and equipment. Because a
radioactive element is often present in submicrogram quantities, a
significant fraction of it may be readily lost by adsorption on the
surface of containers or glassware used in the examination. This
may cause a loss of radioactivity and possible contamination of
subsequent samples due to reuse of inadequately cleansed containers.
A-39
-------
Silica
Apparatus and Materials:
• Polyethylene bottles.
Sample Collection, Preservation, and Handling:
• Collect samples in bottles of polyethylene plastic only; do not use
glassware for any sample handling.
• Store samples at 4°C.
• All samples must be analyzed within 28 days of collection.
Quality Control:
• If samples are stored in glass, silica may leach into the sample and
raise concentrations, therefore glassware cannot be used.
A-40
-------
Solids
Apparatus and Materials:
• Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
• Store samples at 4°C.
• Samples must be analyzed within the following times, according to
the analysis to be performed:
Dissolved 7 days
Volatile Dissolved 7 days
Suspended 7 days
Volatile Suspended 7 days
Total 7 days
Volatile Total 7 days
Settleable 48 hours
Quality Control:
• Sample should be analyzed as soon as possible after collection for
best results.
• Exclude unrepresentative particles such as leaves, sticks, or large
solids.
• Glass bottles are desirable. Plastic bottles are satisfactory
provided that the material in suspension in the sample does not
adhere to the walls of the container. Store samples that are likely
to contain iron or manganese so that oxygen will not come into
contact with the water. Analyze these samples promptly to minimize
the possibility of chemical or physical change during storage.
A-41
-------
Sulfate
Apparatus and Materials:
• Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
• In the presence of organic matter, certain bacteria may reduce
sulfate to sulfide. To avoid this, samples are stored at 4°C.
• All samples must be analyzed within 28 days of collection.
Quality Control:
• No special precautions.
A-42
-------
Sulfide
Apparatus and Materials:
• Polyethylene or glass bottles.
• Zinc Acetate [Zn(C2H39 using NaOH. Fill sample
bottle completely allowing no headspace.
• Store sample at 4°C.
• All samples must be analyzed within 7 days of collection.
Quality Control:
* It is important that all sample bottles are sealed airtight, with no
entrapped air.
A-43
-------
Sulfite
Apparatus and Materials:
• Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
• Collect a fresh water sample, allow as little contact with air as
possible, as air will oxidize the sulfite to sulfate.
• All samples should be analyzed onsite.
Quality Control:
• It is important that all sample bottles be sealed airtight, with no
entrapped air.
A-44
-------
Surfactants
Apparatus and Materials:
• Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
• Store samples at 4°C
• All samples must be analyzed within 48 hours of collection.
Quality Control:
p No special precautions.
A-45
-------
Total Organic Carbon (TOG)
Apparatus and Materials:
• Glass bottles, with Teflon lined caps.
• Cone, hydrochloric acid (HC1) (ACS).
Sample Collection, Preservation, and Handling:
• Acidify samples with cone, hydrochloric acid to a pH of 2.0 or less.
• Store samples at 4°C.
• All samples should be analyzed within 28 days of collection.
Quality Control:
• Avoid exposure of the sample to light and atmosphere, minimize
storage time.
A-46
-------
Total Organic Halide (TOX)
Apparatus and Materials:
• Glass bottles, amber, with Teflon lined caps.
e Sodium sulfite, Na2SC>3, 0. 1 M
Sample Collection, Preservation, and Handling:
• If amber glass bottles are not available, samples should be
protected from light.
• Samples should be stored at 4°C without headspace.
• Reduce residual chlorine by the addition of 1 ml of 0. 1 M sodium
sulfite per liter of sample.
• TOX may increase with storage, therefore, samples should be analyzed
as soon as possible after collection; maximum holding time should
not exceed 7 days.
Quality Control:
• Glassware used in TOX sampling and analysis must be thoroughly
cleaned. All glassware should be washed using detergent and hot
water, rinsed with tap water and, as a final rinse, deionized
water. Drain dry and heat at 105°C for 1 hour. Glassware should be
sealed and stored in a clean area after drying and cooling.
A-47
-------
Turbidity
Apparatus and Materials:
• Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
• Store samples at 4°C.
• All samples must be analyzed within 48 hours of collection.
Quality Control:
• Turbidity analysis should be performed on the day the sample is
taken. If longer storage is unavoidable, store samples in the dark
for up to 48 hours. Prolonged storage before measurement is not
recommended because irreversible changes in turbidity may occur.
A-48
-------
TABLE A-l. RECOMMENDED SAMPLING AND PRESERVATION PROCEDURES FOR WATER AND WASTEWATER
Parameter
Acidity
Alkalinity
Asbestos
Bacteria
Bicarbonate
BOD
^ Bromide
1
vo Carbonate
Chloride
Chlorine Demand
Chromium VI
COD
Color
Conductance
Cyanide
Fluoride
Hardness
Hydrazine
Collection
technique
Grab or composite
Grab or composite
Grab or composite
Grab only
Grab only
Grab only
Grab or composite
Grab only
Grab or composite
Grab only
Grab or composite
Grab only
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Container4
P,G
P,G
P
Pro, G
P,G
P,G
P.G
P,G
P,G
P,G
P,G
P.G
P,G
P,G
P,G
P
P,G
P,G
Preservation
Cool, 4°C
Cool, 4°C
Cool, 4°CC
Cool, 4°C, 10%
Na2S203, EDTA
Determine onsite
Cool, 4°C
None required
Determine onsite
None required
Determine onsite
Cool, 4°C
H2S04 to pH <2; Cool, 4°C
Cool, 4°C
Cool, 4°C
NaOH to pH >12, 0.6g
Ascorbic acid<*
None required
HN03 to pH <2
If not analyzed immediately,
collect under acid. Add
90 ml of sample to 10 ml
(1+9) HC1
Holding timeb
14 days
14 days
48 hours
6 hours
No holding
48 hours
28 days
No holding
28 days
No holding
24 hours
28 days
48 hours
28 days
14 days
28 days
6 months
7 days
Minimum
required
voliyne
(ml)
100
100
1000
200
100
1000
100
100
50
200
100
50
50
100
500
300
100
100
(continued)
-------
TABLE A-l (continued)
Parameter
Iodide
Iodine
Metals (Except Cr VI)
Dissolved
Suspended
Total
>
(01
O Nitrogen
Ammonia
Kjeldahl (total)
Nitrate plus Nitrite
Nitrate
Nitrite
Oil & Grease
Organics
Extractables (base/
neutrals and acids)
Collection
technique
Grab or composite
Grab only
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab only
Grab or composite
Container3 Preservation
P,G Cool 4°C
P,G Determine onsite
P,G Filter onsite, HNC>3 to
pH < 2
P,G Filter onsite
P,G HN03 to pH < 2
P,G Cool, 4°C, H2S04 to
pH <2
P,G Cool, 4°C, H2S04 to
pH <2
P,G Cool, 4°C, H2S04 to
pH <2
P,G Cool, 4°C, H2S04 to
pH<2
P,G Cool, 4°C
G Cool 4°C, H2S04 to
pH<2
G, Teflon- Cool, 4°C
lined cap
Holding time'3
24 hours
No holding
6 months, except
Hg — 28 days
6 months, except
Hg — 28 days
6 months, except
Hg — 28 days
28 days
28 days
28 days
48 hours
48 hours
28 days
7 days until
extraction, 30 days
after extraction
Minimum
required
volume
(ml)
100
500
200
200
100
400
500
100
100
50
1000
1000
(continued)
-------
TABLE A-l (continued)
Parameter
Organics (cont.)
Purgeables (halocarbons-
aromatics)
Purgeables (acrolein and
acrylonitrile)
Pesticides and PCBs
pH
Phenol
Phosphorus
Ortho phosphate
Phosphorus, Total
Radioact ivi ty
Silica
Dissolved
Total
Solids
Dissolved
Volatile Dissolved
Suspended
Collection
technique Container3 Preservation
Grab only G, Teflon- Cool, 4°C
lined cap
Grab only G, Teflon- Cool, 4°C
lined cap
Grab or composite G, Teflon- Cool, 4°C
lined cap
Grab only P,G Determine onsite
Grab or composite G Cool, 4°C, H2S04 to pH <2
Grab or composite P,G Filter onsite, cool, 4°C
Grab or composite P,G Cool, 4°C, H2SC>4 to
pH <2
Grab or composite P,G HN03 to pH <2
Grab or composite P Cool, 4°C
Grab or composite P Cool, 4°C
Grab or composite P,G Cool, 4°C
Grab or composite P,G Cool, 4°C
Grab or composite P,G Cool, 4°C
Minimum
required
volume
Holding time*3 (ml)
14 days
14 days
7 days until
extraction, 30 days
after extraction
2 hours
24 hours
48 hours
28 days
6 months
28 days
28 days
7 days
7 days
7 days
40
40
250
25
500
50
50
1 gal
50
50
100
100
100
(continued)
-------
TABLE A-l (continued)
Parameter
Solids (cont.)
Volatile Suspended
Total
Volatile Total
Settleable
Sulfate
Sulfide
E
"^ Sulfite
Surfactants
TOG
TOX
Turbidity
aP = Polyethylene, G =
''The holding times are
EPA-600/4-82-055 and
Collection
technique Container3
Grab or composite P,G
Grab or composite P,G
Grab or composite P,G
Grab or composite P,G
Grab or composite P,G
Grab or composite P,G
Grab or composite P,G
Grab or composite P,G
Grab or composite G, Teflon-
lined cap
Grab or composite G, Amber,
Teflon-lined
cap
Grab or composite P,G
Glass, Pro = Polypropylene
those listed in Technical Additions to
Methods for Organic Chemical Analysis of
Preservation
Cool, 4°C
Cool, 4°C
Cool, 4°C
Cool, 4°C
Cool, 4°C
Cool, 4°C, 2 ml zinc acetate
plus NaOH to ph > 9
Determine onsite
Cool, 4°C
Cool, 4°C, HC1 to pH < 2
Cool, 4°C, add 1 ml 0.1 M
sodium sulfite
Cool, 4°C
Methods for Chemical Analysis
Minimum
required
volume
Holding time'3 (ml)
7 days
7 days
7 days
48 hours
28 days
7 days
No holding
48 hours
28 days
7 days
48 hours
of Water and Wastes,
100
100
100
100
50
500
50
250
25
100
100
Municipal and Industrial Wastewater, EPA-600/4-82-057.
clf samples cannot be filtered within 48 hours, add 1 ml of a 2.71% solution of mercuric chloride to inhibit bacterial
growth.
QShould only be used in the presence of residual chlorine.
-------
APPENDIX B
EQUIPMENT AVAILABILITY AND FABRICATION
B-l
-------
I. EQUIPMENT AVAILABILITY
Apparatus
Stainless Steel Scoops, Trays, Beakers, Ladles
8,9,15
Thin Wall Tube Samplers, Soil Augers, Hand Corers
45,50
Gravity Corers, Dredges and Grabs
40,45
Thiefs and Triers
9,34
Water Level Indicators
38,45
Down Hole Submersible Probes
23,25,43,51
Bailers, Coliwasa
26,34,48
Peristaltic Pumps
8,9,15,29
Gas Displacement Pumps
5,48
Combustible Gas Detectors
3,13,16,17,33,36,41
Oxygen Monitors
6,13,16,17,33,36,41
Portable Flame lonization Detectors
1,2
Portable Photoionization Detectors
22,37
Stain Detector Tubes
7,17,31,33,35
Personal Sampling Pumps
7,11,14,19,28,32,33,39,46
High Volume Air Samplers
18,39,44
B-2
-------
Radiation Dosimeters
4,10,20,47,49
Radiation Film Badges
12,20,24,42
Radiation Survey Instruments
4,10,12,20,21,27,30,47,49
Vendors
1. Analabs, Inc.
80 Republic Drive
North Haven, CT 06473
(203) 288-8463
2.. Analytical Instrument Development, Inc.
Rt. 41 and Newark Rd.
Avondale, PA 19311
(215) 268-3181
3. Bacharach Instrument Company
301 Alpha Drive
Pittsburgh, PA 15238
(412) 782-3500
4. Baird Atomic
125 Middlesex Turnpike
Bedford, MA 01730
(617) 276-6000
5. BarCad System, Inc.
P.O. Box 424
Concord, MA 01742
(617) 969-0050
6. Beckman Instruments, Inc.
Process Instrument Division
2500 Harbor Boulevard
Fullerton, CA 92634
7. Bendix Corporation
Environmental and Process Instruments Division
P.O. Drawer 831
Ronceverte, WV 24970
(304) 647-4358
8. Cole Palmer
7425 North Oak Park Ave.
Chicago, Illinois 60648
(800) 323-4340
B-3
-------
9. Curtin Matheson Scientific
Major Metropolitan Areas
10. Dosimeter Corporation of America
P.O. Box 42377
Cincinnati, OH 45242
(513) 489-8100
11. DuPont Company
Applied Technology Division
Concord Plaza - Clayton Bldg.
Wilmington, DE 19898
(302) 772-5989
12. Eberline Instruments
P.O. Box 2108
Santa Fe, NM 87501
(505) 471-3232
13. Energetics Science
Six Skyline Drive
Hawthorne, NY 10532
14. Environmental Measurements, Inc.
215 Leidesdorff Street
San Francisco, CA 94111
(415) 398-7664
15. Fisher Scientific
Major Metropolitan Areas
16. Gas Measurement Instruments Ltd.
Inchinnan Estate
RenfrewPA49RG
(041) 812-3211
17. GasTech Inc.
Johnson Instrument Division
331 Fairchild Drive
Mountain View, CA 94043
(415) 967-6794
18. General Metal Works Inc. .
8368 Bridgetown Road
Village of Cleves, OH 45002
(513) 941-2229
19. Gilian Instrument Corp.
1275 Route 23
Wayne, NJ 07470
(201) 696-9244
B-4
-------
20. Gulf Nuclear
202 Medical Center Boulevard
Webster, TX 77598
(713) 332-3581
21. Health Physics Instruments
124 San Felicia Drive
Goleta, CA 93117
(805) 685-2612
22. HNU Systems, Inc.
30 Ossipee Road
Newton Upper Falls, MA 02164
(617) 964-6690
23. Hydrolab Corporation
P.O. Box 9406
Austin, TX 78766
(512) 255-8841
24. ICN Dosimetry Service
26201 Niles Road
Cleveland, OH 44128
(216) 831-3000
25. Industrial & Environmental Analysts Inc.
P.O. Box 626
Essex Junction, VT 05452
(802) 878-5138
26. Johnson Division
UOP, Inc.
St. Paul, MN 55164
(612) 636-3900
27. Johnston Laboratories
P.O. Box 20086
383 Hillen Road
Towson, MD 21204
(301) 337-8700
28. Kurz Instruments Inc.
P.O. Box 849
Carmel Valley, CA 93924
(408) 659-3421
29. Leonard Mold and Die
960 West 48th Avenue
Denver, CO 80221
(303) 433-7101
B-5
-------
30. Ludlum Measurements
P.O. Box 248
Sweetwater, TX 79556
(915) 235-5494
31. Matheson Safety Products
P.O. Box 85
932 Paterson Plank Road
East Rutherford, NJ 07073
(201) 933-2400
32. MDA Scientific, Inc.
1815 Elmdale Ave.
Glenview, IL 60025
33. Mine Safety Appliance Co.
600 Penn Center Boulevard
Pittsburgh, PA 15235
34. Nasco
901 Janesville Ave.
Fort Atkinson, WI 53538
(414) 563-2446
35. National Draeger, Inc.
101 Technology Drive
Pittsburgh, PA 15275
(412) 787-8383
36. National Mine Service Company
Industrial Safety Division
355 N. Old Steubenville Pike
Oakdale, PA 15071
(412) 788-4353
37. Photovac, Incorp.
134 Doncaster Ave.
Unit 2
Thornhill
Ontario, Canada L3T1L3
38. Powers Electric Products Company
P.O. Box 11591
Fresno, CA 93774
39. Research Appliance Company
Moose Lodge Road
Cambridge, MD 21613
(301) 228-9505
B-6
-------
40. Research Instrument Manufacturing Co. Ltd.
RR No. 2 Guelph
Ontario, Canada N1H6H8
(519) 822-1547
41. Rexnord Safety Products/Biomarine Ind.
45 Great Valley Parkway
Malvern, PA 19355
(215) 647-7200
42. R.S. Landauer Jr. Company
Division of Technical Operations, Inc.
Science Road
Glenwood, IL 60425
(312) 755-7000
43. Sensorex
9713 Bolsa Ave.
Westminster, CA 92683
(714) 554-7090
44. Sierra Instruments Inc.
P.O. Box 909
Carmel Valley, CA 93924
(408) 659-3177
45. Soiltest, Inc
2205 Lee Street
Evanston, IL 60202
(312) 869-5500
46. Spectrex Corporation
3594 Haven Ave.
Redwood City, CA 94063
(415) 365-6567
47. Technical Associates
7051 Eton Avenue
Canoya Park, CA 91303
(213) 883-7043
48. Timco Manufacturing Company, Inc.
P.O. Box 35
Prairie Du Sac, WI 53578
(608)-643-8534
49. Victoreen, Inc.
10101 Woodland Ave.
Cleveland, OH 44104
(216) 795-8200
B-7
-------
50. Wildco
301 Cass Street
Saginaw, MI 48602
(517) 799-8100
51. Yellow Springs Instrument Co.
Yellow Springs, OH 45387
(513) 767-7241
B-8
-------
II. EQUIPMENT FABRICATION
Many of the instruments and devices listed previously can also be readily
fabricated in-house. This usually affords considerable cost savings as well
as allows for custom designs and alterations.
Bailers, coliwasas and hand corers can be constructed from available
stainless steel and teflon stock. The diagrams and drawings which accompany
their description in the text show nominal dimensions and construction
materials. Sizes can however be altered to fit particular needs. The sources
cited with these drawings as well as the references at the end of the method
comment further on their construction and use.
The device used in Method IV-12: Sampling of Headspace Gases in Sealed
Vessels, is not currently available through commercial sources. The
fabrication details are therefore included in this Appendix.
B-9
-------
SEALED VESSEL TAPPING DEVICE ASSEMBLY
1. Fabricate mounting plate.
2. Position Portalign on mounting plate, drill 6.4 mm holes through
Portalign base and mounting plate. Tap holes for 7.14 mm thread in
mounting plate. Secure Portalign to mounting plate with 7.14 mm SAE
bolts.
3. Thread ball valve into mounting plate.
4. Thread Swagelok cross assembly onto ball valve.
5. Insert drill bit into chuck of drill.
6. Insert drill into Portalign assembly per manufacturer's instruction.
Pass drill bit through Teflon ferrule.
7. Place part 101-6 so that it stops drill bit travel approximately 10 mm
below bottom of gasket material on mounting plate.
8. Mount entire assembly onto container using standard steel strap packaging
equipment.
9. Place springs over Portalign guide rods.
10. Push springs down until good tension is obtained. Secure with extra
101-6 and 101-8 parts.
11. Finger tighten compression nut containing Teflon ferrules.
B-10
-------
Parts
1. Mounting Plate— 12.7 mm thick x 76 mm wide x 127 mm long, mild steel.
19.1 mm x 3.2 mm deep channel on top of each side. A
6.4 mm NPT hole in center of plate.
Bottom of mounting plate covered with 4.8 mm thick
closed cell Neoprene gasket.
2. Ball Valve—
316 stainless steel, 6.4 mm male NPT thread one end,
6.4 mm female PNT other end.
3. Swagelok Cross— 316 stainless steel, three sides 6.4 mm male NPT,
6.4 mm Swagelok side.
Assemble as Follows:
A. 0-50 psig pressure gauge, 6.4 mm female NPT to
one side of cross.
B. 316 stainless steel, 6.4 mm male NPT to 6.4
Swagelok needle valve, mount opposite pressure
gauge.
C. 6.4 mm Teflon ferrules into 6.4 mm Swagelok
fitting.
4. Drill Bit—
5. Drill—
6. Portalign Drill
Assembly—
4 mm drill bit, 140 mm long, flutes approximately
12 mm long.
Skill Model No. 2002 hand drill, cordless. Wired to
operate remotely at 300 rpm. Interlocked with
microswitch attached to depth stop.
Portalign, Portalign Tool Company, San Diego,
California, as shown below.
B-ll
-------
Parts List
101-1
Portalign drill guide
Additional Parts Required Per Assembly
2 each 101-8 ) ^ „ n .
\ From Portalign
2 each 101-6 '
2 each Springs to fit over guide rods of Portalign approximately
30 kg force each spring when compressed.
B-12
-------
APPENDIX C
PACKING AND SHIPPING GUIDELINES
C-l
-------
I. INTRODUCTION
The Federal Regulations set forth by the Department of Transportation
(DOT) for the packaging, labeling, and shipping of hazardous materials are
extensive and broadly applicable. Therefore, a copy of the DOT requirements
as described in the Code of Federal Regulations, 49 CFR 171-177, is an
essential reference for those anticipating the need to ship samples of
hazardous materials. What follows are generalized guidelines for compliance
with DOT standards, along with references to the applicable sections in the
Federal Register. It may be prudent to check with state and local agencies
for any additional requirements or restrictions they may have.
II. SAMPLE TYPES
In selecting the proper shipping procedures it should first be decided
which of the two basic categories the sample falls into: Environmental Sample
or Hazardous Substance Sample. An additional need for this distinction is to
provide bases for selecting health and safety precautions for the laboratory
personnel receiving and handling the samples.
A. Environmental Samples—These are samples of soil, water, or air
usually collected offsite of a hazardous waste dump or chemical
spill and are therefore not expected to be contaminated with high
concentrations of toxic materials. The function of "environmental
sample" collection is usually to monitor the extent of contamination
and/or the offsite transport of contaminated materials. If there
is doubt as to the suitability of a sample to this classification it
should be placed in the Hazardous Substance category.
B. Hazardous Substances—Samples falling into this group are known or
expected to be contaminated at concentrations that are potentially
harmful; including, but not limited to, onsite samples of soil or
water, samples from drums or bulk storage tanks, contaminated pools,
lagoons, etc., and leachates from hazardous waste sites.
These are operational definitions intended to aid in making decisions
concerning sample handling and shipping. The specifics of the DOT definitions
are found in 40 CFR §§261.3 and 261.4.
III. ENVIRONMENTAL SAMPLES
Although packaging and shipping requirements for environmental samples
(associated with hazardous waste situations) are not as stringent as for
hazardous waste samples, it is recommended that the following general packing
procedure be utilized to ensure safe delivery and maintain sample integrity.
This becomes especially important when samples are being transported by common
carrier. If sufficient information is available concerning the nature of the
sampled material, the following may be relaxed accordingly.
C-2
-------
A. Packing
1. Place sample bottle properly labeled and sealed into a plastic
bag and then into a metal paint can such that the bag is
surrounded on all sides with an absorbent cushioning material,
such as vermiculite. Securely affix top on can.
2. Place a "This Side Up" label on the can top and indicate the
top with arrows on the side of the can.
3. Place a label on the outside of the can specifying
"Environmental Sample."
4. Put a layer of absorbent cushioning material in the bottom of a
hard plastic lined metal cooler.
5. Place cans in the cooler with proper end up and fill in around
the cans with additional absorbent cushioning material.
6. If required, include sealed plastic bags of ice before closing
cooler.
7. Seal the space between the cooler bottom and lid with
fiberglass tape.
8. Make several wraps around the cooler perpendicular to the seal
to assure that the lid will remain closed if the latch is
accidentally released or damaged.
9. Also tape the cooler drain plug so it will not open.
10. Place a complete address label on the lid of the cooler
including the name, address, and phone number of the receiving
laboratory and the return address and phone number of the
shipper (49 CFR §261.4(d)(2)).
11. Place a "This End Up" label on the lid of the cooler and "This
End Up" arrows on all four sides.
12. Secure the contents with a hasp and lock (if cooler is so
equipped) or a custody seal signed and affixed across the
cooler lid and side.
13. This parcel is suitable to be shipped by commercial air cargo
transporter, rail, or truck.
It should be noted that the addition of the following "hazardous" compounds as
preservatives to environmental samples will not alter the Environmental
classification provided the following criteria are met:
C-3
-------
1. Hydrochloric acid solutions at concentrations 0.04 percent
(w/w) or less.
2. Mercuric chloride in water solutions at concentrations less
than or equal to 0.004 percent (w/w).
3. Nitric acid in water, concentrations less than or equal to 0.15
percent (w/w).
4. Sulfuric acid solutions, concentrations less than or equal to
0.035 percent (w/w).
5. Sodium hydroxide in water, concentrations less than or equal to
0.080 percent (w/w).
6. Phosphoric acid in water, concentrations yielding a pH range
between 4 and 2.
IV. HAZARDOUS SUBSTANCE SAMPLES
Samples known or suspected to contain hazardous materials must be
regarded as hazardous substances and be transported in coherence with DOT
requirements. Samples with known or suspected hazardous constituents should
be prepared and shipped as specified in 49 CFR 101, the DOT Hazardous
Materials Table. When the exact nature of a substance is unknown or in
question, a tentative class assignment should be made (49 CFR §§172.402(h) and
173.2) assuming a worst case designation. Start with the most severe
classification of the sequence of precedence (49 CFR §173.2) shown in Table
C-l unless reliable information exists for elimination of that category.
Therefore, a sample would be treated as radioactive unless knowledge of the
sample or radiation detection measurements contradict this classification.
Poison A would then be the next designation to consider, until reliable
information provides for assigning it to the next applicable category. Of the
Poison A group bromoacetone, cyanogen chloride (at temperatures less than
13.1°C), hydrocyanic acid (prussic) solution, methyldichloroarsine, and
phosgene (diphosgene) occur as liquids. If a liquid can, by available
reliable information, be exempted from this category, or if the sample is a
solid then the next designation to apply is Flammable Liquid.
The packaging procedures previously described for environmental samples
are suitable for the flammable liquids and all subsequent categories. There
are additional requirements, however.
1. Sample bottles should be filled allowing sufficient ullage
(approximately 10 percent of volume) to prevent the liquid from
completely filling the bottle at 55°C (130°F).
2. Sample bottles should contain no more than 1 quart of liquid.
3. Labeling on the cooler must include
C-4
-------
TABLE C-l. DOT PRIORITY RANKING OF HAZARDOUS MATERIALS
Category Definition Applicable regulations
General 49 CFR 173.1-173.34, 177
1 Radioactive Material 49 GFR 173.389 49 CFR 173.390-173.398
2 Poison A 49 CFR 173.326 49 CFR 173.327-173.337
3 Flammable Gas 49 CFR 173.300 49 CFR 173.300-173.316
4 Nonflammable Gas 49 CFR 173.300 49 CFR 173.300-173.316
5 Flammable Liquid 49 CFR 173.115 49 CFR 173.116-173.119,
173.121-173.149a
6 Oxidizer 49 CFR 173.151 49 CFR 173.152-173.239a
7 Flammable Solid 49 CFR 173.150 49 CFR 173.152-173.239a
8 Corrosive Material (Liquid) 49 CFR 173.240 49 CFR 173.241-173.299a
9 Poison B 49 CFR 173.343 49 CFR 173.344-173.379
10 Corrosive Material (Solid) 49 CFR 173.240 49 CFR 173.241-173.299a
11 Irritating Materials 49 CFR 173.381 49 CFR 173.381-173.385
12 Combustible Liquid (in 49 CFR 173.115 49 CFR 173.116-173.118a,
containers exceeding 100 173.121-173.149a
gal capacity)
13 ORM-B 49 CFR 173.800 49 CFR 173.510, 173.800-
173.862
14 ORM-A 49 CFR 163.605 49 CFR 173.510, 173.605-
173.655
15 Combustible Liquid (in 49 CFR 173.115 49 CFR 173.116-173.118a,
containers having capacities 173.121-173.149a
of 110 gal or less)
16 ORM-E 49 CFR 173.1300 49 CFR 173.510
C-5
-------
• "Laboratory Samples" label.
• "This End Up" label on lid.
• "This End Up" arrows on all four sides.
• "Flammable Liquid, n.o.s." label ("n.o.s.": not otherwise
specified).
• Address label with name, address, and phone number of receiving
lab; and a return address with the same information for the
sender.
4. Air transport permitted solely on cargo only aircraft.
Sources
1. NEIC Policies and Procedures. EPA-330/9-78-001-R (Revised December 1981),
2. Technical Methods for Investigating Sites Containing Hazardous
Substances. (Draft.) Sampling, Handling, Packaging, and Shipping
Procedures. EPA Technical Monograph No. 22, June, 1981.
3. U.S. Department of Transportation Code of Federal Regulations. 49 CFR.
C-6
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APPENDIX D
DOCUMENT CONTROL/CHAIN-OF-CUSTODY PROCEDURES
D-l
-------
GENERAL
Adherence to strict document control and chain-of-custody procedures is
extremely important especially in relation to surveys at hazardous waste
sites. The legal implications alone demand that accountability be given an
utmost priority. The basic aspects of document control and chain-of-custody
have therefore been included in this section. For additional information, the
following publication, from which this section was developed, should be
consulted.
• NEIC Policies and Procedures Manual, EPA-330-78-001R, May 1978
(revised December 1981), Section II
DOCUMENT CONTROL
The purpose of document control is to assure all project documents will
be accounted for when the project is complete. Document control should
include the use of serialized documents, a document inventory procedure and an
adequate document filing system, all issued by, under the control of, and
maintained by an appointed Document Control Officer (DCO). Table D-l lists
the principal items subject to document control during a specific project.
Serialized Documents
Sample collection and analytical tags, and chain-of-custody records
should have preprinted serial numbers. It is not necessary that a sample tag
number match a custody record number, however, it is necessary that all issued
numbers be appropriately accounted for by the DCO. It is also necessary that
in the event a tag or custody record is damaged, lost or destroyed prior to
its use, its serial number and disposition are recorded.
Other Documents
Other documents used during the conduct of a project (e.g., field
logbooks, laboratory notebooks, data sheets, etc.) should be appropriately
coded with a unique identifier to ensure accountability. The project DCO will
be responsible for development of the document identification system, paying
particular attention to its utility and consistency for the specified
program. An example of a document identification system is as follows:
Subcontractor Code
Project Code (if necessary) Document Code Serial Number
00-000-000- -00- -A- -00001
In addition, a listing of suggested document codes is shown in Table D-2.
D-2
-------
TABLE D-l. DOCUMENTS SUBJECT TO CONTROL
Project Work Plan
Project Logbooks
Field Logbooks
Sample Data Sheets
Sample Tags
Chain-of-Custody Records
Laboratory Logbooks
Laboratory Data, Calculations, Graphs, etc.
Sample Checkout
Sample Inventory
Internal Memos
External Written Communication
Confidential Information
Photographs, Drawings, Maps
Quality Assurance Plan
Litigation Document
Final Report
D-3
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TABLE D-2. SUGGESTED DOCUMENT CODES
Document Code letter
Project Work Plans A
Project Logbooks B
Sampling Logbooks C
Sampling Data Sheets Dl, D2 etc.
Sampling Coding Form E
Laboratory Notebooks G
Laboratory Data Sheets HI, H2 etc.
Sample Logs Ll, L2 etc.
Internal Memos M
External Written Communication N
Confidential Information 0
Photos, Maps, Drawings P
QA Plan Q
Reports R
Final Report FR
Miscellaneous X
D-4
-------
CHAIN-OF-CUSTODY
The primary need for the implementation of chain-of-custody procedures
stems from the possibility that a sample or a piece of data derived from the
collection of a sample will be used as physical evidence in an enforcement
action. The purpose of chain-of-custody in these instances is to trace the
possession of a sample from the time of collection, until it or the derived
data is introduced as evidence in legal proceedings. Custody records should,
therefore, trace a sample from its collection, through all transfers of
custody, until it is delivered to the analytical laboratory. At this point,
internal laboratory records should document sample custody until its final
disposition.
In order to establish that a sample is valid, it is also necessary to
document the measures taken to prevent and/or detect tampering—either to the
sample itself, the sampling equipment used or the environment sampled. This
is done by the use of evidence tape, locks and custody seals, and documented
entries noting their condition in field and laboratory log books. The custody
record must document any tampering that may have occurred; the absence of any
such comments indicates no tampering observed or noticed during the period of
custody.
Since it may not always be possible to know ahead of time if a sample
will be used as evidence in future legal actions, it is a good common sense
practice to institute a proper chain-of-custody in all instances. Use of such
practices as standard operating procedures on a project to project basis will
contribute to the consistency and quality of the generated data.
Sample Identification
Preprinted, preserialized sample collection tags are recommended to
identify samples collected for shipment to the analytical laboratory.
Specific analysis tags may also be issued by the analytical laboratory after
the sample has arrived. All collected samples, including duplicates and field
blanks should be completely filled in with a minimum of the following
information:
• Project Code )
\ Assigned by the
• Location Number ) Document Control Officer (DCO)
• Date of Collection
• Time of Collection
• Location Description
• Signature of Sampler
D-5
-------
• Lab Sample Number—Assigned by the Analytical Laboratory
• Remarks Section
An example of an appropriate sample collection tag is shown in Figure D—1.
After sample analysis and appropriate quality assurance checks have been
made, original sample collection tags are to be stored in a document file
maintained by the DCO and the tag serial number is recorded in a master log
for future reference. Maintaining such files and records is an important
aspect of sample traceability and provides a needed cross referencing tool
that can be used to correlate any one of the identifying numbers and sources
(e.g., collection tag, laboratory number, master log, etc.) with a specific
sample.
Chain-of-Custody Forms
There are many transfers of custody during the course of a sampling
program, from time of collection through final sample disposition, and all
samples should be accompanied by a Chain-of-Custody Record to document these
transfers. In some instances, such as in the collection of air samples on
solid sorbents, it becomes necessary to initiate custody procedures from
collection media preparation on as the sorbent itself becomes part of the
sample after collection is complete. Laboratories providing QC samples must
also initiate a custody record. The use of a customized record sheet, such as
the one shown in Figure D-2 fulfills these requirements by providing a
convenient format for recording pertinent information.
The custody records are used for a packaged lot of samples; more than one
sample will usually be recorded on one form. More than one custody record
sheet may be used for one package, if necessary. Their purpose is to document
the transfer of a group of samples traveling together; when the group of
samples changes, a new custody record is initiated. The original of the
custody record always travels with the samples; the initiator of the record
keeps the copy. When custody of the same group of samples changes hands
several times, some people will not have a copy of the custody record. This
is acceptable as long as the original custody record shows that each person
who had received custody has properly relinquished it.
In general, the following procedures should be followed when using the
custody record sheets.
• The originator fills in all requested information from the sample
tags (except in the case of air collection media and external QC
samples which will be accompanied by custody forms from the
originating facility).
• The person receiving custody checks the sample tag information
against the custody record. He also checks sample condition and
notes anything unusual under "Remarks" on the custody form.
D-6
-------
3
A
?
BL
CD
V
a
Z
o
3
^
2.
Z
e
CONTRACT NO:
DESIGNATE
COMP
GRAB
SOURCE
Phosphate
CO
J"1!
1
o
TEMPERATURE
|
1
I
g
z
z
3
8
z
z
0
z
pH
o
o
a
0
Radioactivity
DATE
TIME
PRESERVATIVE
SAMPLER (Signature):
S
00
o
o
1
o
a
1
o
5T
o
o»
H
m
3
17
Pesticides/PC
W
m
O
•
1
o
Q
ANALYS
m
O
o
o
Figure D-l. Sample Collection Tag.
D-7
-------
CHAIN OF CUSTODY RECORD
Project Code
Project Nimc
SAMPLERS (Signature)
REMARKS
U
I
00
Relinquished by (Signature)
Relinquished by (Signature)
Relinquished by (Signature)
Date/Time
Date/Time
Date/Time
Received by (Signature)
Relinquished fay (Signature)
Received by (Signature)
Relinquished by (Signature)
Received for Laboratory by
(Signature)
Date/Time
Date/Time
Date/Time
Remarks
Received by (Signature)
Received by (Signature)
N 1000
Figure D-2. Chain-of-Custody Form.
-------
• The originator signs in the top left "Relinquished by" box and keeps
the copy.
• The person receiving custody signs in the adjacent "Received by" box
and keeps the original.
• The Date/Time will be the same for both signatures since custody
must be transferred to another person.
• When custody is transferred to the Sample Bank or an analytical
laboratory, blank signature spaces may be left and the last
"Received by" signature box used. Another approach is to run a line
through the unused signature boxes.
• In all cases, it must be readily seen that the same person receiving
custody has relinquished it to the next custodian.
» If samples are left unattended or a person refuses to sign, this
must be documented and explained on the custody record.
Receipt for Samples Form
When it becomes necessary to split samples with another source, a
separate receipt for samples form (Figure D-3) is prepared and marked to
indicate with whom the samples have been split. The signature of the person
receiving the samples is required and if this person refuses to sign, it
should be noted in the "Received by" space.
This form also complies with requirements of both Section 3007(a)(2) of
RCRA and Section 104 of the Comprehensive Environmental Response Compensation
and Liability Act. These sections both state that "...If the officer,
employee or representative obtains any samples prior to leaving the premises,
he shall give to the owner, operator, or agent-in-charge a receipt describing
the samples obtained and, if requested, a portion of such sample equal in
volume or weight to the portion retained." A copy of the completed form must
be given to one of the above described individuals, even if the offer for
split samples is declined.
Custody Seals
Custody seals are narrow strips of adhesive paper used to demonstrate
that no tampering has occurred. They may be used on sampling equipment or a
house door, but they are intended for use on a sample transport container
which is not secured by a padlock. They are not intended for use on
individual sample containers.
D-9
-------
RECEIPT FOR SAMPLES
PROJ NO
PROJECT NAME
SAMPLERS (Signature)
Split Samples Offered
( ) Accepted ( ) Declined
STA NO
DATE
TIME
COUP
(D
<
oc
o
SPLIT
SAMPLES
TAG NUMBERS
Name of Facility
Facility Location
STATION DESCRIPTION
Transferred by (Signature)
Date Time
NO OF
CON-
TAINERS
REMARKS
Received by fSigntture) Telephone
Title Date Time
O
I
Distribution Original to Coordinator Field Files, Copy to Facility
N 349
Figure D-3. Receipt for Sample form.
-------
Laboratory Custody Procedures
An onsite sample bank, the sampling laboratory area and any analytical
laboratory used for analyses are considered to be working "laboratories"
subject to laboratory custody procedures. Each laboratory should have a
designated sample custodian who implements a system to maintain control of the
samples.
This includes accepting custody of arriving samples, verifying that
information on the sample tags match the Chain-of-Custody Record, assigning
unique laboratory numbers and laboratory sample tags and distributing the
samples to the analyst.
The designated custodian is also responsible for retaining all original
identifying tags, data sheets and laboratory records as part of the permanent
project file.
Questions/Problems Concerning Custody Records
If a discrepancy between sample tag numbers and custody record listings
is found, the person receiving custody should document this and properly store
the samples. The samples should not be analyzed until the problem is resolved.
The responsible person receiving custody should attempt to resolve the
problem by checking all available information (other markings on sample
container, type of sample, etc.). He should then document the situation on
the custody record and in his project logbook and notify the project QA
Manager by the fastest available means, followed by written notification.
Changes may be written in the "Remarks" section of the Custody record and
should be initialed and dated. A copy of this record should accompany the
written notification to the QA Manager.
D-ll
-------
APPENDIX E
APPLICABLE TABLES
E-l
-------
TABLE E-l. RANDOM NUMBERS
03
97
16
12
55
16
84
63
33
57
18
26
23
52
37
70
56
99
16
31
47
74
76
56
59
22
42
01
21
60
18
62
42
36
85
29
62
49
08
16
43
24
62
85
56
77
17
63
12
86
07
38
40
28
94
17
18
57
15
93
73
67
27
99
35
94
53
78
34
32
92
97
64
19
35
12
37
22
04
32
86
62
66
26
64
39
31
59
29
44
46
75
74
95
12
13
35
77
72
43
36
42
56
96
38
49
57
16
78
09
44
84
82
50
83
40
96
88
33
50
96
81
50
96
54
54
24
95
64
47
17
16
97
92
39
33
83
42
27
27
47
14
26
68
82
43
55
55
56
27
16
07
77
26
50
20
50
95
14
89
36
57
71
27
46
54
06
67
07
96
58
44
77
11
08
38
87
45
34
87
61
20
07
31
22
82
88
19
82
54
09
99
81
97
30
26
75
72
09
19
46
42
32
05
31
17
77
98
52
49
79
83
07
00
42
13
97
16
45
20
98
53
90
03
62
37
04
10
42
17
83
11
45
56
34
89
12
64
59
15
63
32
79
72
43
93
74
50
07
46
86
46
32
76
07
51
25
36
34
37
71
37
78
93
09
23
47
71
44
09
19
32
14
31
96
03
93
16
68
00
62
32
53
15
90
78
67
75
38
62
62
24
08
38
88
74
47
00
49
49
INSTRUCTIONS FOR THE USE OF THE RANDOM NUMBER TABLE
1. Number the members of the lot (i.e., the drums onsite, the sections
within a grid) in a numerical order.
2. Decide on the number of samples necessary. This should be a number
sufficient to give statistical significant data. Ten to 20 percent is
usually adequate. This number should be predetermined in the test plan
or should coincide with the time and equipment available.
3. Using the set of random numbers above; choose any number as a starting
point, then proceed to select the next number in any predetermined
direction (i.e., down the column, across the rows) until the selection
process has yielded the desired number of samples.
E-2
-------
Example:
Soil samples are to be collected from a field 10 meters by 15 meters in
area. Equipment and laboratory arrangements have been made to handle eight
samples.
A. The area is divided into an imaginary 1 meter grid.
B. Each quadrant in the grid is assigned a number in a numerical
order; West to East, North to South (or left to right, top to
bottom).
C. Referring to the Random Number table it is arbitrarily decided to
start at the first number in the third row, then proceed down the
column.
This would result in the selection of 43 as the first number
followed by 24, 62, 85, 56, 77, 17 and 63 as the eighth and final
selection.
The grids corresponding to these numbers would then be sampled.
E-3
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TABLE E-2. CONVERSION FACTORS/TABLES OF MEASUREMENT
MISCELLANEOUS
kilo —means one thousand
cmli —means one-hundredth
mini —means one-thousandth
micro — means one-milhonlti
Length and area
1 Mamie mile (mi) -- 5280 feet
= 1 609 kilometers
1 loot (ft) =12 inches
=-- 30 48 centimeters
l inch (in ) = 25 40 millimeters
100 ft per mm - 0 508 meter per sec
1 squire foot -- 144 sq inches
= 0 0929 sq meter
' sq.iare inch - 6 45 sq centimcicrs
'. niior.ii;.or \kiii) - 1COO meters
= 0 621 statute mile
1 .neter (m) = 100 centimeters (cm)
- 1000 millimeters (mm)
= 1 094 yards
- 3 281 feet
- 39 37 inches
1 cmtuneter ^ 1 x 108 angstroms (A')
1 micron = 0 001 millimeter
- 0 000039 inch
1 mete' per sec =-- 193 9 ft per mm
Weight
1 U 3 long ton -- 2210 pounds
- 101*5 kilograms
' U S ;ho.-t ten - ?OCO pounds
- 907 kilograms
1 pound (I b) 16 ounces
-= 7000 grams
-- 0 -,54 kilogram
-'. ''cc (Ci) u dorl'j oound
- 28 J5 grams
1 kg per in in - ' g;,,!), pe, |,ier
- I IV, 1 i, ; thous-r;!
1 g per r,j m =1 my prr I irr
~ 1 pa;! p'-i mti'un
(pp'ii)
1 PP"i -- 6 33 liver million gal
1 uja:n per gal -- M3 l» p,r million gal
1 b per million gal =012 |,ym
1 IbnerrpiMior gai - 0 00 / cum pe' gjilon
1 II) pe' thousand - 120 pprn "
gal
Pressure
1 atmosphere = 760 mm (29 92 m )
mercury with density
13 595 grams per cc
1 gram
1 pouno per loot --
1 metric ton
(tonne)
=-
1 kilogiam (kg)
=
1 gram (g)
1 kg per meter
Volume
1 cubic yard
1 cubic foot
1 cubic inch
1 imperial gallo'i ->
1 U S gallon
1 U S ba're!
ipetrcieu'"!
1 cubic meter
(cu m)
1 liter
1 atmospnerp
(menu
1 Ib per square foot -
1 IS per square
inch
=
-
1 ton per square -
inch
1 inch head of
water
64 8 milligrams
0 C023 ounce
1 488 kg per me'er
1000 kilograms
0 S84 long ton
i 102 U S bhort tons
2205 pounds
1000 grams
2 205 pounds
10CO milligram (mg)
0 03527 ounce
15 43 grains
0 672 pound per ft
27 cu ft
0 755 cu m
i 728 cu in
2S 32 liters
7 ?3 U 5 gallons
16 39 cu centi-
meters (cu cm)
277 -1 cu in
1 55 'iters
0 (J33 imperial
gallon
3 /85 liters
231 cu m
0 1337 cu ft
4? u S gilim*,
jf) •, perir.i qallon;
10.X1 users
j; U cu ft
ICi'.O cc
0 T ''M impoi lal
'1 0(1
0 A :' U S gj.'L.i
61 0 cu m
14 MP 1!) per si] i.)
1 0,n Ki] ; IT :,q cm
1 kg pi1' -.q cni
10 flOU krj ppi <;q m
10 in lu\i;i el w.itei
14 22 It) po- sq in
0 1921 in of v,aler
4 88 kg pt'i sq in
2 036 in head of
mercury
2 309 ft hcaJ of
water
0 0703 k'j pe; sq an
0 0690 t>ar
1 406 kg per sq mm
5 20 It) per sq h
1 board foot = 12 m x 12 m x 1 in.
thick
= 144 cu in
1 cu ft pe' mm = 1 699 cu m per hour
1 cu m per hour - 0 589 cu ft per mm
1 cu ft per sec = 646,316 gallons per
day
--- 448 83 gallons per
mm
1 gallon per mm - 0 00144 million
gallons per day
Density (weight/volume)
1 cu ft per Ib -- 0 0624 cu m per kg
1 Ib per cu ft = '6 0? kg p-r cu m
1 grim per CM 'I - 2 268 grams p:r cu m
1 gram per U S -- 17 11 grams per cu m
gallon = 1711 mg.'liter
1 cu m per kg = 16 02 cu ft per Ib
1 kg per cu m =0 0624 Ib per cu ft
1 gram per cu m -- 0 437 grain per cu ft
-= 0 0584 grain per U S
gallon
1 gram per cc = 62 4 Ib per ru ft
1 gram per liter - 58 4 grams per U S
gallon
Water at 62 F (16.7 C)
I cubic foot = 62 3 ft
1 pound -- 0 01604 Cu ft
t U S gal'un --- 8 34 Ib
Water at 39 2 F (4 C),
nmimum (loi sity
1 cubic too! 62 4 Ib
1 cubic mi'ta - 1COO kg
1 pound - 0 01602 cu ft
1 liter --- 1 0 kg
1 fool tii-.id of - 0 43J l;j |,r. •... ,
water
1 m he.nl of *,itei 0 1 kq pi" ; q ,„,
1 n head 01 -- 0 4'11 ib ni M;
mercury
1 m head of -- 1 360 \ q p"i • •• t
mercuiy
1 kilogram per sq - 1 inm hr.id o| \, ,•,
m -- 0 2048 Ib pe' MJ n
1 kilogram per sq --- 735 5 nun u- m.... , .,
cm ^ 14 22 Ib pi'' ''i •
1 kg per sq mm --= 0711 ion per v, i<,
In these conversions, inches and If-i of
water are measured at 62 F (16 7 C) n,.l
hmeters anU meters ol water at 39 2 (- 1 1 Ct
and inches, millimeters and mete's ol rncr
curyat32 F (0 C),
Source: Betz Handbook of Industrial Water Conditioning, 1976
seventh edition, Betz Laboratories, Inc., Trevose, PA
U S. Environmental Protection Agency
Region 5, Library ;PL~12J>
77 West Jackson Boulevard, 12th Floor
Chicago, IL 60504-3590
E-4
irU.S GOVERNMENT PRINTING OFFICE. 1983—659-095/0746
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